CN103772294A - Phenoxyl pyrilamine compound and application - Google Patents
Phenoxyl pyrilamine compound and application Download PDFInfo
- Publication number
- CN103772294A CN103772294A CN201210412091.0A CN201210412091A CN103772294A CN 103772294 A CN103772294 A CN 103772294A CN 201210412091 A CN201210412091 A CN 201210412091A CN 103772294 A CN103772294 A CN 103772294A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- halo
- carbonyl
- acid
- alkoxy
- 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.)
- Granted
Links
- 0 C*(C)(C)Cc1cnc(C)[s]1 Chemical compound C*(C)(C)Cc1cnc(C)[s]1 0.000 description 5
- STRIHVJHJCROTB-UHFFFAOYSA-N CCC(C)Cc1ccc(C)nc1 Chemical compound CCC(C)Cc1ccc(C)nc1 STRIHVJHJCROTB-UHFFFAOYSA-N 0.000 description 1
- INERIPFNXNZTKG-UHFFFAOYSA-N CCc1ncnc(NC(C)c(cn2)ccc2Oc2ccccc2)c1Cl Chemical compound CCc1ncnc(NC(C)c(cn2)ccc2Oc2ccccc2)c1Cl INERIPFNXNZTKG-UHFFFAOYSA-N 0.000 description 1
- ZBUFWVTUQBTTEF-UHFFFAOYSA-N Cc1cc(N)cc(C2CC2)c1 Chemical compound Cc1cc(N)cc(C2CC2)c1 ZBUFWVTUQBTTEF-UHFFFAOYSA-N 0.000 description 1
- YIDUVRHFPFLCLN-UHFFFAOYSA-N Cc1ncnc(O)c1Cl Chemical compound Cc1ncnc(O)c1Cl YIDUVRHFPFLCLN-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
Abstract
The invention discloses a phenoxyl pyrilamine compound which has a structural general formula I as shown in the specification, wherein definitions of substituents in the formula are as shown in the specification. The compound has broad-spectrum bactericidal, insecticidal and acaricidal activity, has excellent prevention and control effects on diamondback moths, armyworms, myzus persicae and tetranychus cinabarinus boisdu, and particularly has the better prevention effect on the myzus persicae and the tetranychus cinabarinus boisdu. The compound shows the good bactericidal activity at the same time, and a part of the compound has the excellent prevention and control effects on diseases such as cucumber downy mildew, wheat powdery mildew, puccinia sorghi and rice blast at a very low dose.
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 disclose following compound general formula and particular compound CK1 (numbering in two patents is respectively compound 47 and compd A), have 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 discloses above-claimed cpd (being numbered compound 5 in document), and the raw result of surveying shows that wheat rust and barley powdery mildew are had to certain activity.
CK1(fluorine mepanipyrim)
Patent JP11012253, JP11049759, EP0665225 disclose and in following Compound C K2(JP11012253, have been numbered compound 7) preparation method, the English popular name Flufenerim of this compound, the phonetic worm amine of Universal Chinese character name.
The phonetic worm amine of CK2()
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 have reported 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, the also active report of lifeless matter.
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 had certain sterilization, killed mite and/or insecticidal activity, and wherein TABLE 1 the 209th row has been mentioned Compound C K16, CK17, CK18, but reports without any biological activity;
Document Bioorganic & Medicinal Chemistry Letters, 2007.17:260-265 has reported that following general formula compound is as novel human immunodeficiency virus HIV-1(Human Immunodeficiency Virus) inhibitor use.
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 0 to 4 integer; In the time that m is greater than 1, R
3can be identical 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
12alkylthio carbonyl C
1-C
12alkyl, halo C
1-C
12alkylthio carbonyl 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 0 to 5 integer; In the time that n is greater than 1, R
4can be identical or different;
R
5, R
6can be identical or different, be selected from respectively hydrogen, halogen, C
1-C
12alkyl, C
1-C
12alkoxyl group or C
3-C
12cycloalkyl; Or R
5, R
6with the carbon composition C being 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
12thiazolinyl sulfenyl, 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
12alkyl sulfonyl-amino carbonyl, C
1-C
12alkyl-carbonyl-amino alkylsulfonyl, C
3-C
12cycloalkyl oxy carbonyl, 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
12alkynyloxy group carbonyl, 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 unsubstituted or that further replaced by the following group of 1-5
1-C
6alkyl, (mixing) aryl carbonyl, (mixing) aryloxycarbonyl, (mixing) aryl C
1-C
6alkyl oxy carbonyl, (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
9can be identical or different, be selected from respectively hydrogen, C
1-C
12alkyl or halo C
1-C
12alkyl;
Be selected from-CH of A
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 0 to 4 integer; In the time that m is greater than 1, R
3can be identical 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
6alkylthio carbonyl C
1-C
6alkyl, halo C
1-C
6alkylthio carbonyl 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 0 to 5 integer; In the time that n is greater than 1, R
4can be identical or different;
R
5, R
6can be identical or different, be selected from respectively hydrogen, halogen, C
1-C
6alkyl, C
1-C
6alkoxyl group or C
3-C
6cycloalkyl; Or R
5, R
6with the carbon composition C being 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
9can be identical or different, be selected from respectively hydrogen, C
1-C
6alkyl or halo C
1-C
6alkyl;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
The further preferred compound of the present invention 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 0 to 4 integer; In the time that m is greater than 1, R
3can be identical 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
4alkylthio carbonyl C
1-C
4alkyl, halo C
1-C
4alkylthio carbonyl 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 0 to 5 integer; In the time that n is greater than 1, R
4can be identical or different;
R
5, R
6can be identical or different, be selected from respectively hydrogen, halogen, C
1-C
4alkyl, C
1-C
4alkoxyl group or C
3-C
6cycloalkyl; Or R
5, R
6with the carbon composition C being 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
9can be identical or different, be selected from respectively hydrogen, C
1-C
4alkyl or halo C
1-C
4alkyl;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
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 1 to 2 integer;
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 0 to 5 integer;
R
5, R
6can be identical or different, be selected from respectively 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;
R
7be selected from hydrogen;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
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 independently of one another respectively hydrogen, fluorine, chlorine or bromine; M is selected from 1 to 2 integer;
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 1 to 5 integer;
R
5, R
6can be identical or different, be selected from respectively hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy;
R
7be selected from hydrogen;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
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 1 to 5 integer;
Be selected from-CH of A
2-;
Or the salt of compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or trifluoroacetic acid formation.
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-, be selected from-CH of A
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 4-chlorine, 3, the chloro-4-trifluoromethyl of 5-dichloro, 4-trifluoromethyl or 2-, be selected from-CH of A
2-;
Or the salt of above-claimed cpd and hydrochloric acid formation.
In the definition of the compound of Formula I providing, collect term General Definition used as follows above:
Halogen: refer to fluorine, chlorine, bromine or iodine.Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl, normal-butyl or the tertiary butyl.Cycloalkyl: replace or unsubstituted cyclic alkyl, for example cyclopropyl, cyclopentyl or cyclohexyl.Substituting group is as methyl, halogen etc.Haloalkyl: straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc.Alkyl sulphinyl: straight or branched alkyl is connected in structure through sulfinyl (SO-), as methylsulfinyl.Haloalkyl sulfinyl: straight or branched alkyl sulphinyl, the hydrogen atom on its alkyl can partly or entirely be replaced by halogen atom.Halogenated alkyl sulfonyl: straight or branched alkyl sulphonyl, the hydrogen atom on its alkyl can partly or entirely be replaced 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-.
Alkyl sulfonyl-amino carbonyl: alkyl-SO
2-NH-CO-.Alkyl-carbonyl-amino alkylsulfonyl: alkyl-CO-NH-SO
2-.Alkyl-carbonyl alkyl: alkyl-CO-alkyl-.Alkyl sulphonyl oxygen base: alkyl-S (O)
2-O-.Alkoxy carbonyl: alkyl-O-CO-, as CH
3oCO-, C
2h
5oCO-.Cycloalkyl oxy carbonyl: 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 be replaced by halogen atom.For example, chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc.Halo alkoxy carbonyl: the hydrogen atom on the alkyl of alkoxy carbonyl can partly or entirely be replaced by halogen atom, as ClCH
2cH
2oCO-, CF
3cH
2oCO-etc.Alkoxyalkyl: alkyl-O-alkyl-, for example CH
3oCH
2-.Halogenated alkoxy alkyl: the hydrogen atom on the alkyl of alkoxyalkyl can partly or entirely be replaced by halogen atom, as ClCH
2cH
2oCH
2-, CF
3cH
2oCH
2-etc.Alkoxy carbonyl alkyl: alkoxy carbonyl-alkyl-, for example CH
3oCOCH
2-.Alkoxyl group alkoxy carbonyl: as CH
3o CHx
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 be replaced by halogen atom.For example, chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group etc.Alkylthio alkyl: alkyl-S-alkyl-, for example CH
3sCH
2-.Halogenated alkylthio alkyl: the hydrogen atom on the alkyl of alkylthio alkyl can partly or entirely be replaced 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.Haloalkyl amino: straight or branched alkylamino, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom.Dialkyl amido: as (CH
3)
2n-, (CH
3cH
2)
2n-.Thiazolinyl: straight or branched alkene class, for example vinyl, 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomer.Thiazolinyl also comprises polyenoid class, as 1,2-propadiene base and 2,4-hexadienyl.Haloalkenyl group: straight or branched alkene class, the hydrogen atom on these thiazolinyls can partly or entirely be replaced by halogen atom.Alkene oxygen base: straight or branched alkene class, is connected in structure through Sauerstoffatom key.Haloalkene oxygen base: straight or branched alkene oxygen base, the hydrogen atom on these alkene oxygen bases can partly or entirely be replaced by halogen atom.Thiazolinyl sulfenyl: 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, for example ethynyl, 1-proyl, 2-propynyl and different butynyl, pentynyl and hexin base isomer.Alkynyl also comprises the group being made up of multiple triple bonds, as 2,5-hexadiyne base.Halo alkynyl: straight or branched alkynes class, the hydrogen atom on these alkynyls can partly or entirely be replaced by halogen atom.Alkynyloxy group: straight or branched alkynes class, is connected in structure through Sauerstoffatom key.Halo alkynyloxy group: straight or branched alkynyloxy group, the hydrogen atom on these alkynyloxy groups can partly or entirely be replaced by halogen atom.Alkynyloxy group carbonyl: 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 be replaced by halogen atom.Alkyl-carbonyl: alkyl is connected in structure through carbonyl, as CH
3cO-, CH
3cH
2cO-.Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can partly or entirely be replaced by halogen atom, as CF
3cO-.Alkoxy carbonyl: alkoxyl group is connected in structure through carbonyl.As CH
3oCO-, CH
3cH
2oCO-.Alkyl amino-carbonyl: alkyl-NH-CO-, for example 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 one or more N, O, the heteroatomic five-ring of 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-chlorophenoxy carbonyl, 4-nitrophenoxy carbonyl, naphthyloxy carbonyl etc.Arylalkyl oxygen base carbonyl: as benzyl oxygen base carbonyl, 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 have been enumerated respectively R in general formula I
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 1R
1substituting group
Table 2R
2substituting group
| R 2 | R 2 | R 2 | R 2 |
| F | Cl | Br | I |
Table 3R
3substituting group
| R 3 | R 3 | R 3 | R 3 |
| H | CH 3 | i-C 4H 9 | OC 4H 9-n |
| F | C 2H 5 | t-C 4H 9 | OC 4H 9-i |
| Cl | n-C 3H 7 | OCH 3 | OC 4H 9-t |
| Br | i-C 3H 7 | OC 2H 5 | OCF 3 |
| I | n-C 4H 9 | OC 3H 7-n | OCH 2CF 3 |
| OH | s-C 4H 9 | OC 3H 7-i | OCF 2CF 3 |
Table 4 (R
4) n substituting group
| (R 4)n | (R 4)n | (R 4)n | (R 4)n | (R 4)n |
| H | 4-CH 3 | 3-CH 2OCH 3 | 2,6-2Cl-4-CONH 2 | 2-CF 3-4-Br-6-NO 2 |
| 2-F | 2,3-2CH 3 | 4-CH 2OCH 3 | 2,4-2Cl-6-NO 2 | 3-NO 2-4-CF 3 |
| 3-F | 2,4-2CH 3 | 2-OCOCH 3 | 2,4-2Cl-6-CN | 2-NO 2-4-CN-5-CF 3 |
| 4-F | 2,5-2CH 3 | 3-OCOCH 3 | 2,4-2Cl-6-CF 3 | 2-NO 2-4-CF 3-5-CN |
| 2,3-2F | 2,6-2CH 3 | 4-OCOCH 3 | 2,4-2F-6-NO 2 | 4-OCF 3-2,6-2Br |
| 2,4-2F | 3,4-2CH 3 | 2-OCOCH 2CH 3 | 2,6-2F-4-NO 2 | 2-CH 3-4-Cl-5-CH 2CO 2C 2H 5 |
| 2,5-2F | 3,5-2CH 3 | 3-OCOCH 2CH 3 | 2-NO 2-4-F | 2,4-2Cl-3-CH 3 |
| 2,6-2F | 2-C 2H 5 | 4-OCOCH 2CH 3 | 2-NO 2-4-Br | 2,4-2Cl-3-CH 3-6-NO 2 |
| 3,4-2F | 3-C 2H 5 | 2-OCO 2CH 3 | 2-NO 2-4-CF 3 | 2-Cl-3-CH 3 |
| 3,5-2F | 4-C 2H 5 | 3-OCO 2CH 3 | 2-NO 2-4-CN | 2-CH 3-3-Cl |
| 2,3,4-3F | 2-CF 3 | 4-OCO 2CH 3 | 2-NO 2-4-COCH 3 | 2-CH 3-3-Cl-4,6-2NO 2 |
| 2,3,5-3F | 3-CF 3 | 2-OCH 2OCH 3 | 2-NO 2-4-CONH 2 | 2-CH 3-3-Cl-4-NO 2 |
| 2,4,5-3F | 4-CF 3 | 3-OCH 2OCH 3 | 2-NO 2-4-CH 3 | 2-CH 3-3-Cl-6-NO 2 |
| 2,3,6-3F | 2-OCH 3 | 4-OCH 2OCH 3 | 2-NO 2-4-OCH 3 | 2-Cl-3-CH 3-4,6-2NO 2 |
| 2,4,6-3F | 3-OCH 3 | 2-OCF 2OCF 3 | 2-NO 2-4-SCH 3 | 2-Cl-3-CH 3-4-NO 2 |
| 3,4,5-3F | 4-OCH 3 | 3-OCF 2OCF 3 | 2-NO 2-4-NCH 3 | 2-Cl-3-CH 3-6-NO 2 |
| 2-Cl | 2-SCH 3 | 4-OCF 2OCF 3 | 2-F-4-NO 2 | 2-Br-4-NO 2-6-CN |
| 3-Cl | 3-SCH 3 | 2-COPh | 2-Br-4-NO 2 | 3-Cl-4-CF 3-2,6-2NO 2 |
| 4-Cl | 4-SCH 3 | 3-COPh | 2-CF 3-4-NO 2 | 2NO 2-4,5-2Cl |
| 2,3-2Cl | 2-OCF 3 | 4-COPh | 2-CN-4-NO 2 | 2-NO 2-3,5-2Cl |
| 2,4-2Cl | 3-OCF 3 | 2-COCH 2Ph | 2-COCH 3-4-NO 2 | 2,5-2Cl-4-NO 2 |
| 2,5-2Cl | 4-OCF 3 | 3-COCH 2Ph | 2-CONH 2-4-NO 2 | 2,5-2Cl-6-NO 2 |
| 2,6-2Cl | 2-SCF 3 | 4-COCH 2Ph | 2-CH 3-4-NO 2 | 2,3-2Cl-4-NO 2 |
| 3,4-2Cl | 3-SCF 3 | 2-NHPh | 2-Cl-4-F-6-NO 2 | 2,3-2Cl-6-NO 2 |
| 3,5-2Cl | 4-SCF 3 | 3-NHPh | 2-Cl-4-Br-6-NO 2 | 3,4-2Cl-2,6-2NO 2 |
| 2,3,4-3Cl | 2-OC 2H 5 | 4-NHPh | 2-Cl-4-CH 3-6-NO 2 | 2,5-2Cl-4,6-2NO 2 |
| 2,3,5-3Cl | 3-OC 2H 5 | 2-OPh | 2-Cl-4-CF 3-6-NO 2 | 2,4,5-3Cl-6-NO 2 |
| 2,4,5-3Cl | 4-OC 2H 5 | 3-OPh | 2-Cl-4,6-2NO 2 | 2,3,4-3Cl-5-NO 2 |
| 2,3,6-3Cl | 2-NHCH 3 | 4-OPh | 2-Cl-4-CN-6-NO 2 | 2,3,4-3Cl-6-NO 2 |
| 2,4,6-3Cl | 3-NHCH 3 | 2-CONHPh | 2-Cl-4-OCF 3-6-NO 2 | 2,3,5-3Cl-4,6-2CN |
| 3,4,5-3Cl | 4-NHCH 3 | 3-CONHPh | 2-F-4-Cl-6-NO 2 | 2,5-2Cl-4-OCF 2OCF 3 |
| 2-Br | 2-N(CH 3) 2 | 4-CONHPh | 2-Br-4-Cl-6-NO 2 | 2,6-2Br-4-NO 2 |
| 3-Br | 3-N(CH 3) 2 | 2-CO 2Ph | 2-CH 3-4-Cl-6-NO 2 | 2-F-4-NO 2-6-Cl |
| 4-Br | 4-N(CH 3) 2 | 3-CO 2Ph | 2-CF 3-4-Cl-6-NO 2 | 2-Cl-4-NO 2-6-SCN |
| 2,3-Br | 2-COCH 3 | 4-CO 2Ph | 4-Cl-2,6-2NO 2 | 2-Br-4-NO 2-6-Cl |
| 2,4-2Br | 3-COCH 3 | 2-CONH 2 | 2-CF 3-4-CN | 2-Cl-4-NO 2-6-OCH 3 |
| 2,5-2Br | 4-COCH 3 | 3-CONH 2 | 2-CN-4-CF 3 | 2-Cl-4-NO 2-6-SCH 3 |
| 2,6-2Br | 2-COC 2H 5 | 4-CONH 2 | 4-CF 3-2,6-2NO 2 | 2-Cl-4-NO 2-6-NHCH 3 |
| 3,4-2Br | 3-COC 2H 5 | 2-Cl-4-F | 4-CN-2,6-2NO 2 | 2-Cl-4-NO 2-6-SO 2CH 3 |
| 3,5-2Br | 4-COC 2H 5 | 2-Cl-4-Br | 4-CH 3-2,6-2NO 2 | 2-Cl-4-SO 2CH 3 |
| 2,3,4-3Br | 2-SO 2CH 3 | 2-Cl-4-CH 3 | 4-OCF 3-2,6-2NO 2 | 2,6-2Cl-4-SO 2CH 3 |
| 2,3,5-3Br | 3-SO 2CH 3 | 2-Cl-4-CF 3 | 4-OCH 3-2,6-2NO 2 | 2,6-2Cl-4-CH 3 |
| 2,4,5-3Br | 4-SO 2CH 3 | 2-Cl-4-NO 2 | 4-SCH 3-2,6-2NO 2 | 2,6-2Cl-4-CO 2CH 3 |
| 2,3,6-3Br | 2-OCHF 2 | 2-Cl-4-CN | 4-NHCH 3-2,6-2NO 2 | 2,6-2Cl-4-CONHCH 3 |
| 2,4,6-3Br | 3-OCHF 2 | 2-Cl-4-OCF 3 | 4-F-2,6-2NO 2 | 2,6-2Cl-4-CON(CH 3) 2 |
| 3,4,5-3Br | 4-OCHF 2 | 2-F-4-Cl | 2-CF 3-4,6-2NO 2 | 2,6-2Cl-4-CF(CF 3) 2 |
| 2-CN | 2-SO 2C 2H 5 | 2-Br-4-Cl | 2-CN-4,6-2NO 2 | 2-Cl-4-CF(CF 3) 2-6-Br |
| 3-CN | 3-SO 2C 2H 5 | 2-CH 3-4-Cl | 2-CH 3-4,6-2NO 2 | 2-F-4-CF(CF 3) 2-6-Br |
| 4-CN | 4-SO 2C 2H 5 | 2-CF 3-4-Cl | 2-F-4,6-2NO 2 | 2-F-4-CF(CF 3) 2-6-Cl |
| 2-NO 2 | 2-CO 2CH 3 | 2-NO 2-4-Cl | 2-OCF 3-4,6-2NO 2 | 2,4,5-3Cl-3,6-2CN |
| 3-NO 2 | 3-CO 2CH 3 | 2-CN-4-Cl | 2-CF 3-4-Br | 2,3,5-3F-4,6-2CN |
| 4-NO 2 | 4-CO 2CH 3 | 2-OCF 3-4-Cl | 3-CF 3-4-NO 2 | 2-SO 2NH 2 |
| 2,4-2NO 2 | 2-CO 2C 2H 5 | 2,6-2Cl-4-NO 2 | 2-CN-4-Cl-6-NO 2 | 3-SO 2NH 2 |
| 2,4,6-3NO 2 | 3-CO 2C 2H 5 | 2,6-2Cl-4-CF 3 | 2-OCF 3-4-Cl-6-NO 2 | 4-SO 2NH 2 |
| 2-CH 3 | 4-CO 2C 2H 5 | 2,6-2Cl-4-CN | 3-CF 3-4-CN | |
| 3-CH 3 | 2-CH 2OCH 3 | 2,6-2Cl-4-COCH 3 | 3-CN-4-CF 3 |
Table 5R
5(R
6) substituting group
Table 6R
7substituting group
| R 7 | R 7 | R 7 | R 7 |
| H | OH | CH 3 | C 2H 5 |
| n-C 3H 7 | i-C 3H 7 | n-C 4H 9 | s-C 4H 9 |
| i-C 4H 9 | t-C 4H 9 | HCO | CH 3CO |
| CH 3CH 2CO | n-C 3H 7CO | i-C 3H 7CO | CH 3SO 2 |
| CH 3CH 2SO 2 | n-C 3H 7SO 2 | n-C 4H 9SO 2 |
Part of compounds of the present invention can illustrate by the particular compound of listing in table 7-table 47, and wherein showing 7-table 38 be general formula I A compound, and showing 39-table 47 is general formula I B compound, but the present invention only limits 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
6when=H, (R
4) n be different substituting group in table 7, representation compound is numbered 1-278.
Table 7
| Sequence number | (R 4)n | Sequence number | (R 4)n | Sequence number | (R 4)n |
| 1 | H | 2 | 2-F | 3 | 3-F |
| 4 | 4-F | 5 | 2,3-2F | 6 | 2,4-2F |
| 7 | 2,5-2F | 8 | 2,6-2F | 9 | 3,4-2F |
| 10 | 3,5-2F | 11 | 2,3,4-3F | 12 | 2,3,5-3F |
| 13 | 2,4,5-3F | 14 | 2,3,6-3F | 15 | 2,4,6-3F |
| 16 | 3,4,5-3F | 17 | 2-Cl | 18 | 3-Cl |
| 19 | 4-Cl | 20 | 2,3-2Cl | 21 | 2,4-2Cl |
| 22 | 2,5-2Cl | 23 | 2,6-2Cl | 24 | 3,4-2Cl |
| 25 | 3,5-2Cl | 26 | 2,3,4-3Cl | 27 | 2,3,5-3Cl |
| 28 | 2,4,5-3Cl | 29 | 2,3,6-3Cl | 30 | 2,4,6-3Cl |
| 31 | 3,4,5-3Cl | 32 | 2-Br | 33 | 3-Br |
| 34 | 4-Br | 35 | 2,3-Br | 36 | 2,4-2Br |
| 37 | 2,5-2Br | 38 | 2,6-2Br | 39 | 3,4-2Br |
| 40 | 3,5-2Br | 41 | 2,3,4-3Br | 42 | 2,3,5-3Br |
| 43 | 2,4,5-3Br | 44 | 2,3,6-3Br | 45 | 2,4,6-3Br |
| 46 | 3,4,5-3Br | 47 | 2-CN | 48 | 3-CN |
| 49 | 4-CN | 50 | 2-NO 2 | 51 | 3-NO 2 |
| 52 | 4-NO 2 | 53 | 2,4-2NO 2 | 54 | 2,4,6-3NO 2 |
| 55 | 2-CH 3 | 56 | 3-CH 3 | 57 | 4-CH 3 |
| 58 | 2,3-2CH 3 | 59 | 2,4-2CH 3 | 60 | 2,5-2CH 3 |
| 61 | 2,6-2CH 3 | 62 | 3,4-2CH 3 | 63 | 3,5-2CH 3 |
| 64 | 2-C 2H 5 | 65 | 3-C 2H 5 | 66 | 4-C 2H 5 |
| 67 | 2-CF 3 | 68 | 3-CF 3 | 69 | 4-CF 3 |
| 70 | 2-OCH 3 | 71 | 3-OCH 3 | 72 | 4-OCH 3 |
| 73 | 2-SCH 3 | 74 | 3-SCH 3 | 75 | 4-SCH 3 |
| 76 | 2-OCF 3 | 77 | 3-OCF 3 | 78 | 4-OCF 3 |
| 79 | 2-SCF 3 | 80 | 3-SCF 3 | 81 | 4-SCF 3 |
| 82 | 2-OC 2H 5 | 83 | 3-OC 2H 5 | 84 | 4-OC 2H 5 |
| 85 | 2-NHCH 3 | 86 | 3-NHCH 3 | 87 | 4-NHCH 3 |
| 88 | 2-N(CH 3) 2 | 89 | 3-N(CH 3) 2 | 90 | 4-N(CH 3) 2 |
| 91 | 2-COCH 3 | 92 | 3-COCH 3 | 93 | 4-COCH 3 |
| 94 | 2-COC 2H 5 | 95 | 3-COC 2H 5 | 96 | 4-COC 2H 5 |
| 97 | 2-SO 2CH 3 | 98 | 3-SO 2CH 3 | 99 | 4-SO 2CH 3 |
| 100 | 2-OCHF 2 | 101 | 3-OCHF 2 | 102 | 4-OCHF 2 |
| 103 | 2-SO 2C 2H 5 | 104 | 3-SO 2C 2H 5 | 105 | 4-SO 2C 2H 5 |
| 106 | 2-CO 2CH 3 | 107 | 3-CO 2CH 3 | 108 | 4-CO 2CH 3 |
| 109 | 2-CO 2C 2H 5 | 110 | 3-CO 2C 2H 5 | 111 | 4-CO 2C 2H 5 |
| 112 | 2-CH 2OCH 3 | 113 | 3-CH 2OCH 3 | 114 | 4-CH 2OCH 3 |
| 115 | 2-OCOCH 3 | 116 | 3-OCOCH 3 | 117 | 4-OCOCH 3 |
| 118 | 2-OCOCH 2CH 3 | 119 | 3-OCOCH 2CH 3 | 120 | 4-OCOCH 2CH 3 |
| 121 | 2-OCO 2CH 3 | 122 | 3-OCO 2CH 3 | 123 | 4-OCO 2CH 3 |
| 124 | 2-OCH 2OCH 3 | 125 | 3-OCH 2OCH 3 | 126 | 4-OCH 2OCH 3 |
| 127 | 2-OCF 2OCF 3 | 128 | 3-OCF 2OCF 3 | 129 | 4-OCF 2OCF 3 |
| 130 | 2-COPh | 131 | 3-COPh | 132 | 4-COPh |
| 133 | 2-COCH 2Ph | 134 | 3-COCH 2Ph | 135 | 4-COCH 2Ph |
| 136 | 2-NHPh | 137 | 3-NHPh | 138 | 4-NHPh |
| 139 | 2-OPh | 140 | 3-OPh | 141 | 4-OPh |
| 142 | 2-CONHPh | 143 | 3-CONHPh | 144 | 4-CONHPh |
| 145 | 2-CO 2Ph | 146 | 3-CO 2Ph | 147 | 4-CO 2Ph |
| 148 | 2-CONH 2 | 149 | 3-CONH 2 | 150 | 4-CONH 2 |
| 151 | 2-Cl-4-F | 152 | 2-Cl-4-Br | 153 | 2-Cl-4-CH 3 |
| 154 | 2-Cl-4-CF 3 | 155 | 2-Cl-4-NO 2 | 156 | 2-Cl-4-CN |
| 157 | 2-Cl-4-OCF 3 | 158 | 2-F-4-Cl | 159 | 2-Br-4-Cl |
| 160 | 2-CH 3-4-Cl | 161 | 2-CF 3-4-Cl | 162 | 2-NO 2-4-Cl |
| 163 | 2-CN-4-Cl | 164 | 2-OCF 3-4-Cl | 165 | 2,6-2Cl-4-NO 2 |
| 166 | 2,6-2Cl-4-CF 3 | 167 | 2,6-2Cl-4-CN | 168 | 2,6-2Cl-4-COCH 3 |
| 169 | 2,6-2Cl-4-CONH 2 | 170 | 2,4-2Cl-6-NO 2 | 171 | 2,4-2Cl-6-CN |
| 172 | 2,4-2Cl-6-CF 3 | 173 | 2,4-2F-6-NO 2 | 174 | 2,6-2F-4-NO 2 |
| 175 | 2-NO 2-4-F | 176 | 2-NO 2-4-Br | 177 | 2-NO 2-4-CF3 |
| 178 | 2-NO 2-4-CN | 179 | 2-NO 2-4-COCH 3 | 180 | 2-NO 2-4-CONH 2 |
| 181 | 2-NO 2-4-CH 3 | 182 | 2-NO 2-4-OCH 3 | 183 | 2-NO 2-4-SCH 3 |
| 184 | 2-NO 2-4-NCH 3 | 185 | 2-F-4-NO 2 | 186 | 2-Br-4-NO 2 |
| 187 | 2-CF 3-4-NO 2 | 188 | 2-CN-4-NO 2 | 189 | 2-COCH 3-4-NO 2 |
| 190 | 2-CONH 2-4-NO 2 | 191 | 2-CH 3-4-NO 2 | 192 | 2-Cl-4-F-6-NO 2 |
| 193 | 2-Cl-4-Br-6-NO 2 | 194 | 2-Cl-4-CH 3-6-NO 2 | 195 | 2-Cl-4-CF 3-6-NO 2 |
| 196 | 2-Cl-4,6-2NO 2 | 197 | 2-Cl-4-CN-6-NO 2 | 198 | 2-Cl-4-OCF 3-6-NO 2 |
| 199 | 2-F-4-Cl-6-NO 2 | 200 | 2-Br-4-Cl-6-NO 2 | 201 | 2-CH 3-4-Cl-6-NO 2 |
| 202 | 2-CF 3-4-Cl-6-NO 2 | 203 | 4-Cl-2,6-2NO 2 | 204 | 2-CF 3-4-CN |
| 205 | 2-CN-4-CF 3 | 206 | 4-CF 3-2,6-2NO 2 | 207 | 4-CN-2,6-2NO 2 |
| 208 | 4-CH 3-2,6-2NO 2 | 209 | 4-OCF 3-2,6-2NO 2 | 210 | 4-OCH 3-2,6-2NO 2 |
| 211 | 4-SCH 3-2,6-2NO 2 | 212 | 4-NHCH 3-2,6-2NO 2 | 213 | 4-F-2,6-2NO 2 |
| 214 | 2-CF 3-4,6-2NO 2 | 215 | 2-CN-4,6-2NO 2 | 216 | 2-CH 3-4,6-2NO 2 |
| 217 | 2-F-4,6-2NO 2 | 218 | 2-OCF 3-4,6-2NO 2 | 219 | 2-CF 3-4-Br |
| 220 | 3-CF 3-4-NO 2 | 221 | 2-CN-4-Cl-6-NO 2 | 222 | 2-OCF 3-4-Cl-6-NO 2 |
| 223 | 3-CF 3-4-CN | 224 | 3-CN-4-CF 3 | 225 | 2-CF 3-4-Br-6-NO 2 |
| 226 | 3-NO 2-4-CF 3 | 227 | 2-NO 2-4-CN-5-CF 3 | 228 | 2-NO 2-4-CF 3-5-CN |
| 229 | 4-OCF 3-2,6-2Br | 230 | 2-CH 3-4-Cl-5-CH 2CO 2C 2H 5 | 231 | 2,4-2Cl-3-CH 3 |
| 232 | 2,4-2Cl-3-CH 3-6-NO 2 | 233 | 2-Cl-3-CH 3 | 234 | 2-CH 3-3-Cl |
| 235 | 2-CH 3-3-Cl-4,6-2NO 2 | 236 | 2-CH 3-3-Cl-4-NO 2 | 237 | 2-CH 3-3-Cl-6-NO 2 |
| 238 | 2-Cl-3-CH 3-4,6-2NO 2 | 239 | 2-Cl-3-CH 3-4-NO 2 | 240 | 2-Cl-3-CH 3-6-NO 2 |
| 241 | 2-Br-4-NO 2-6-CN | 242 | 3-Cl-4-CF 3-2,6-2NO 2 | 243 | 2NO 2-4,5-2Cl |
| 244 | 2-NO 2-3,5-2Cl | 245 | 2,5-2Cl-4-NO 2 | 246 | 2,5-2Cl-6-NO 2 |
| 247 | 2,3-2Cl-4-NO 2 | 248 | 2,3-2Cl-6-NO 2 | 249 | 3,4-2Cl-2,6-2NO 2 |
| 250 | 2,5-2Cl-4,6-2NO 2 | 251 | 2,4,5-3Cl-6-NO 2 | 252 | 2,3,4-3Cl-5-NO 2 |
| 253 | 2,3,4-3Cl-6-NO 2 | 254 | 2,3,5-3Cl-4,6-2CN | 255 | 2,5-2Cl-4-OCF 2OCF 3 |
| 256 | 2,6-2Br-4-NO 2 | 257 | 2-F-4-NO 2-6-Cl | 258 | 2-Cl-4-NO 2-6-SCN |
| 259 | 2-Br-4-NO 2-6-Cl | 260 | 2-Cl-4-NO 2-6-OCH 3 | 261 | 2-Cl-4-NO 2-6-SCH 3 |
| 262 | 2-Cl-4-NO 2-6-NHCH 3 | 263 | 2-Cl-4-NO 2-6-SO 2CH 3 | 264 | 2-Cl-4-SO 2CH 3 |
| 265 | 2,6-2Cl-4-SO 2CH 3 | 266 | 2,6-2Cl-4-CH 3 | 267 | 2,6-2Cl-4-CO 2CH 3 |
| 268 | 2,6-2Cl-4-CONHCH 3 | 269 | 2,6-2Cl-4-CON(CH 3) 2 | 270 | 2,6-2Cl-4-CF(CF 3) 2 |
| 271 | 2-Cl-4-CF(CF 3) 2-6-Br | 272 | 2-F-4-CF(CF 3) 2-6-Br | 273 | 2-F-4-CF(CF 3) 2-6-Cl |
| 274 | 2,4,5-3Cl-3,6-2CN | 275 | 2,3,5-3F-4,6-2CN | 276 | 2-SO 2NH 2 |
| 277 | 3-SO 2NH 2 | 278 | 4-SO 2NH 2 |
Table 8: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=R
5=R
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 279-556, the 1-278 of successively corresponding table 7.
Table 9: in general formula I A, as W=H, R
1=CH
3, R
2=R
3=Cl, R
5=R
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 557-834, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 835-1112, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1113-1390, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1391-1668, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1669-1946, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1947-2224, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 4727-5004, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5005-5282, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5283-5560, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5561-5838, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5839-6116, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 6117-6394, the 1-278 of successively corresponding 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
6when=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 6395-6672, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 1-278 of successively corresponding 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, the 8897-9036 of successively corresponding table 39.
Table 41: in general formula I B, work as R
1=CH
3, R
2=Cl, (R
4) when n=4-Cl, substituent R
7consistent with table 39, representation compound is numbered 9177-9316, the 8897-9036 of successively corresponding table 39.
Table 42: in general formula I B, work as R
1=C
2h
5, R
2=Cl, (R
4) when n=4-Cl, substituent R
7consistent with table 39, representation compound is numbered 9317-9456, the 8897-9036 of successively corresponding table 39.
Table 43: in general formula I B, work as R
1=CH
3, R
2=Cl, (R
4) n=2, when 4-2Cl, substituent R
7consistent with table 39, representation compound is numbered 9457-9596, the 8897-9036 of successively corresponding table 39.
Table 44: in general formula I B, work as R
1=C
2h
5, R
2=Cl, (R
4) n=2, when 4-2Cl, substituent R
7consistent with table 39, representation compound is numbered 9597-9736, the 8897-9036 of successively corresponding 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, the 8897-9036 of successively corresponding 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, the 8897-9036 of successively corresponding table 39.
The salt of part of compounds of the present invention can illustrate with the salt of the particular compound of listing in table 47, but not limit the present invention.
Table 47 part of compounds salt
The compounds of this invention is prepared (in formula, each group unless otherwise indicated defines ditto) in accordance with the following methods:
The first situation, works as R
7when=H, the preparation of general formula (I-1) compound can adopt following two kinds of methods:
Method one: the pyrimidine chlorine of replacement and the reaction of corresponding replacement amine, reaction formula is as follows.Synthetic method is with reference to EP0370704, EP0356158, EP0264217, EP0665225, JP10036355, US4985426.
The compound of general formula of the present invention (I-1) representative can be made by the amine condensation in suitable solvent shown in the substituted pyrimidines chlorine shown in general formula (II) and general formula (III).Reaction 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.Reaction can have alkali or alkali-free to carry out under existing, and in the time having alkali to react under existing, 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 can, in room temperature between solvent boiling point temperature, be generally 20 ~ 110 ° of C.Reaction times is 30 minutes to 20 hours, common 1 ~ 10 hour.
Substituted pyrimidines cl part shown in general formula (II) has commercially available, or can be according to US4977264, Journal of the American Chemical Society, 79,1455(1957), Journal ofChemical Society, pp.3478-3481(1955) in the method described synthetic.
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, OrganicSyntheses; 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 than the alkyl chain of the few carbon of A.
In suitable solvent, under suitable alkali exists, general formula (IV) reacts with (V), processes and obtain (VI).Concrete preparation can be with reference to fine chemistry industry, and 2005,22 (12): the method for describing in 944-960 is carried out.Reaction is carried out to solvent boiling point temperature range in room temperature conventionally, and more suitable temperature of reaction is 20 ~ 100 ℃.Reaction times is 30 minutes to 20 hours, common 1 ~ 10 hour.The optional acetone freely of suitable solvent, butanone, tetrahydrofuran (THF), acetonitrile, toluene, dimethylbenzene, benzene, DMF, methyl-sulphoxide, methyl alcohol or ethanol etc.The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine or sodium hydride etc.
In suitable solvent, (VI) under suitable catalyzer and ammoniacal liquor existence, obtain (III) through hydrogenating reduction.Concrete preparation can reference literature J.Am.Chem.Soc, and 70,3788 (1948); 82,681 (1960); 82,2386 (1960); Can.J.Chem, 49,2990(1971); J.Org.Chem, 37,335 (1972); Organic Syntheses, Coll.Vol.3, p.229, p.720 (1955); Vol.23, p.71 (1943) or Vol.27, the method for p.18 describing in (1947) is carried out.Reaction is carried out to solvent boiling point temperature range in room temperature conventionally, and more suitable temperature of reaction is 20 ~ 100 ℃.Reaction times is 30 minutes to 20 hours, common 1 ~ 10 hour.Suitable solvent can be selected from methyl alcohol, ethanol, Virahol, benzene,toluene,xylene, acetone, methylethylketone, mibk, chloroform, methylene dichloride, methyl acetate, ethyl acetate, tetrahydrofuran (THF), diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.Suitable catalyzer can be selected from Raney's nickel, palladium carbon or platinum oxide etc.
(2) prepare amine and salt thereof take the Uteramin that replaces as raw material:
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) react in 0 ~ 100 ℃, first make the Uteramin (VIII) of Boc protection.Preferably 0 ~ 50 ℃ of temperature of reaction; Reaction times is 30 minutes to 20 hours, preferably 0.5 ~ 10 hour.Suitable solvent is selected from benzene,toluene,xylene, chloroform, methylene dichloride, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.; Suitable alkali is selected from alkaline carbonate for example sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus.
Then, by (VIII) with (V) in suitable solvent, under the existence of suitable alkali, obtain (IX) in 0 ~ 100 ℃ of condensation reaction.30 minutes to 20 hours reaction times, preferably 0.5 ~ 10 hour.Suitable solvent is selected from benzene,toluene,xylene, chloroform, methylene dichloride, acetone, butanone, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.; Suitable alkali is selected from such as sodium hydride of alkalimetal hydride, for example sodium hydroxide of alkali metal hydroxide or potassium hydroxide, for example sodium carbonate of alkaline carbonate or salt of wormwood, for example pyridine of organic amine or triethylamine.
(IX) in suitable solvent, obtain corresponding salt (X) through suitable sour deprotection, then alkalize to obtain (III).Preferably 0 ~ 50 ℃ of temperature of reaction; Reaction times is 30 minutes to 20 hours, preferably 0.5 ~ 10 hour.Suitable solvent is selected from ethyl acetate, methyl acetate, methyl-formiate, benzene,toluene,xylene, chloroform, methylene dichloride, water, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.; Suitable acid is selected from hydrochloric acid, trifluoroacetic acid, sulfuric acid, acetic acid, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, lauric acid, stearic acid, fumaric acid, toxilic acid, phenylformic acid or phthalic acid etc.; Described alkali is selected from such as sodium hydride of alkalimetal hydride, for example sodium hydroxide of alkali metal hydroxide or potassium hydroxide; For example sodium carbonate of alkaline carbonate or salt of wormwood, for example pyridine of organic amine or triethylamine.Concrete preparation method is referring to WO2004093800A and US20050096485.
Method two: the reaction of the pyrimidine chlorine of replacement and corresponding replacement Uteramin, and then with intermediate (V) condensation, can obtain object (I-1), reaction formula is as follows:
The compound of general formula (I-1) representative can make (XI) by the Uteramin condensation in suitable solvent shown in the substituted pyrimidines chlorine shown in general formula (II) and general formula (VII), then makes (I-1) by (XI) with intermediate (V) condensation under the effect of alkali.Other each group definition are the same.
(II) carry out in suitable solvent with condensation reaction (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 have alkali or alkali-free to carry out under existing, and in the time having alkali to react under existing, 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 can, in room temperature between solvent boiling point temperature, be generally 20 ~ 100 ° of C.Reaction times is 30 minutes to 20 hours, common 1 ~ 10 hour.
(XI) making carries out in suitable solvent with condensation reaction (V), 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 have alkali exist under 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 can, in room temperature between solvent boiling point temperature, be generally 20 ~ 200 ° of C.Reaction times is 30 minutes to 20 hours, common 1 ~ 10 hour.Concrete preparation method is referring to JP11049759, EP0370704, EP0196524, US4895849.
Substituted pyrimidines chlorine (II), part has commercially available, or can be synthetic to literature method according to institute in method one.
Other raw material sources related 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 be with reference to as Publication about Document preparation: 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 obtains corresponding salt I-A with organic acid or inorganic acid reaction, 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 mineral acid salt-forming reaction are carried out to solvent boiling point temperature range in room temperature conventionally, and more suitable temperature of reaction is 20 ~ 100 ℃.Reaction times is 30 minutes to 20 hours, common 1 ~ 10 hour.Suitable solvent can be selected from 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 for example, 3-the third disulfonic acid, tosic acid or Witco 1298 Soft Acid etc.; And mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or carbonic acid etc.Further preferred hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid or phenylformic acid etc.
Although disclosed some compound all belongs to pyrimidinamine compound in compound of Formula I of the present invention and prior art, but constitutional features still exists remarkable difference, and because making compound of the present invention, these structural differences there is better sterilization and/or pesticide and miticide actility.
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 that compound of Formula I is used as the purposes of preparing sterilant, Insecticiding-miticiding agent medicine in agricultural or other field.
The example of the disease of mentioning below is only used for illustrating the present invention, but never limits the present invention.
Compound of Formula I can be used for preventing and treating following disease: Oomycete disease, 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, spinach oidium, radish oidium, downy mildew of garpe, onion mildew), white rust (white rust of colza, cabbage white blister), samping off (rape samping off, tobacco samping off, 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 anthrax, 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 (corn circle pintas, bluish dogbane waist folding is sick, rice blast, the black sheath disease of chestnut, 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 disease, 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 white powder disease, 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 sclerotium disease, 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, compared with still thering is good prevention effect under low dosage.
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 (Acanthoscelidesobtectus) (common pea weevil), the narrow lucky fourth of Chinese wax (Agrilus planipennis) (emerald ash borer, Agrilus planipennis), acupuncture needle Eimeria kind (Agriotesspp.) (wireworm), Anoplophora glabripenis (Anoplophora glabripennis) (Asia psacotheahilaris), cotton boll resembles and belongs to kind of (Anthonomusspp.) (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 (Bruchusspp.) (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)), the long flat ostomatid in angle (Cryptolestes pusillus) (flat ostomatid), the flat ostomatid of Turkey (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 (Cylindrocpturusadspersus) (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 (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), the little stupid genus kind of tooth (Ips spp.) (sour jujube shin little stupid (engravers)), lasioderma serricorne (Lasioderma serricorne) (cigarette beetle), colorado potato bug (Leptinotarsa decemlineata) (Colorado colorado potato bug), Liogenys fuscus, Liogenys suturalis, rice water weevil (Lissorhoptrus oryzophilus) (rice water weevil), the stupid genus kind of powder (Lyctus spp.) (the stupid beetle of wooden stupid moth/powder (powder post beetles)), Maecolaspis joliveti, Megascelis belongs 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) (common 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 (Phyllophaga spp.) (chafer in May/June), 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 (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 is moistened (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), the alfalfa fly (Agromyza frontella) (alfalfa dive fly (alfalfa blotch leafminer)) of diving, Hippelates kind ((Agromyza spp.) (Liriomyza), press 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 Anastrepha kind (Ceratitis spp.) (fruit bat), little of Mediterranean Sea trypetid (Ceratitis capitata) (medfly), Chrysops kind (Chrysops spp.) (deer horsefly), Callitroga's kind (Cochliomyiaspp.) (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 (Melophagusovinus) (sheepked), fly belongs to kind of (Musca spp.) (housefly (a muscid fly)), face fly (Musca autumnalis) (face fly (facefly)), 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 blossommidge)), tatukira (stomoxys calcitruns) (tatukira (stable fly)), the gadfly belongs to kind of (Tahanus spp.) (horse botfly) and 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)), the pretty fleahopper (Calocoris norvegicus) of potato (potato fleahopper (potato mirid)), cimex hemipterus (Cimex hemipterus) (cimex hemipterus (tropical bed bug)), bedbug (Cimexlectularius) (bedbug (bed hug)), Daghertus fasciatus, Dichelops furcatus, the cotton red stinkbug of black wing (Dysdercussuturellus) (red cotton bug (cotton stainer)), Edessa meditabunda, Europe Eurygasterspp (Eurygaster maura) (paddy worm (cerealbug)), Euschistus heros, brown smelly stinkbug (Euschistus 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 bug belongs to kind of (Lygusspp.) (fleahopper (a 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 stinkbug), 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)/the hunt stinkbug (kissing bug) of sucking blood).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), spiral aleyrodid (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), the two tail aphids (Brachycolusnoxius) (Russian aphid (Russian aphid)) of wheat, officinalis tubule aphid (Brachycorynclia asparagi) (officinalis aphid (asparagusaphid)), Brevennia rehi, brevicoryne brassicae (Brevicoryne brassicae) (Caulis et Folium Brassicae capitatae aphid), lecanium belongs to kind of (Ceroplastesspp.) (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 (Dysaphisplantaginea) (rosy apple aphid), green jassids belongs to kind of (Empoasca spp.) (leafhopper), apple aphid (Eriosomalanigerum) (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 brownplanthopper), 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 (Myzuspersicae) (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) (brownplanthopper), chaff sheet armored scale (Parlatoria pergandii) (chaff scale), ebony armored scale (Parlatoria ziziphi) (ebonyscale), 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 budscale), 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-backedplanthopper), 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 (Trialeurodesvaporariorum) (greenhouse whitefly (greenhouse whitefly)), knot wing trialeurodes vaporariorum (Trialeurodesabutiloneus) (bandedwing whitefly), point armored scale belongs to kind of (Unaspis spp.) (a red-spotted lizard), vow sharp clam (Unaspisyanonensis) (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 (carpenterant)), Diprion kind (Diprion spp.) (sawfly (sawfly)), ant belongs to kind of (Formica spp.) (ant), Argentine ant (Iridomyrmex humilis) (Argentineant), Monomorium subspecies (Monomorium ssp.), MonomoriumMayr (Monomoriumminumum) (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 (odoroushouse ant)), Tetramorium kind (Tetranomorium spp.) (Pavement Ant (pavement ant)), Vespula kind (Vespulaspp.) (yellow jacket (yellowjacket)) and Xylocopa kind (Xylocopa spp.) (carpenter bee (carpenter bee)).
Isoptera (Isoptera) (termite): formosanes belongs to kind of (Coptotcrmcs spp.), a bent jaw termite (Coptotermes
Curvignathus), France termite (Coptotermes frenchii), Coptotermes formosanus Shtrari． (Coptotermes formosanus) (Formosansubterranean 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 dwell termite (desertsubterranean 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 dwell termite), Reticulitermes banyulensis, meadow reticulitermes flavipe (Reticulitermes grassei), yellow limb reticulitermes flavipe (Reticulitermes flavipes) (east soil dwell termite), beautiful little Huang reticulitermes flavipe (Reticulitermes hageni), west reticulitermes flavipe (Reticulitermes hesperus) (west soil dwell termite), Sang Te reticulitermes flavipe (Reticulitermes santonensis), northern reticulitermes flavipe (Reticulitermes speratus) dwells, 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, Amyelosistransitella (navel orangeworm), Anacamptodes defectaria, sliver gelechiid (Anarsia lineatella) (peach twigborer), jute bridge night high (Anomis sabulijera) (jute looper), Anticarsia (Anticarsia gemmatalis) (velvetbeancaterpillar), fruit tree leaf roller (Archips argyrospila) (fruit tree leafroller), rose leaf roller (Archips rosana) (rose leaf roller), volume moth belongs to kind of (Ar gyrotaenia spp.) (a tortricid moths), tangerine Argyrotaenia spp (Argyrotaeniacitrana) (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 (peachfruit moth)), straw borer spp kind (Chilo spp.), Chlumetia transversa Walker (Chlumetia transversa) (mango shootborer), rose Choristoneura spp (Choristoneura rosaceana) (oblique banded leafroller), Noctua kind (Chrysodeixisspp.), cnaphalocrocis medinalls guenee (Cnaphalocerus medinalis) (meadow leaf roller (grass leafroller)), beans Pier kind (Coliasspp.), 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) (peamoth), 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), Southwest Maize bar crambid (Diatraea graniosella) (southwester cornborer), 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) (lightbrown 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 (Ephestiakuehniella) (Mediterranean flour moth), Epimeces belongs to kind of (an Epimeces spp.), steinernema at night (Epinotiaaporema), 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 (Feltiaspp.) (cutworm), angle sword Noctua kind (Gortyna spp.) (stem borer), east moth fruit moth (Grapholita molesta) (the sub-heart-eating worm of peach (apricot) (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), the real noctuid (Helicoverpa zea) of paddy (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 eggplant wild snout moth's larva (Leucinodes orbonalis) of white wing (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.) (tentcaterpillars), lopper worm (Mamestra brassicae) (dish march moth (cabbage armyworm)), the wild snout moth's larva of beanpod (Marucatestulalis) (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 (Ostrinianubilalis) (European corn borer (European corn borer)), Oxydia vesulia, the brown volume moth of boundary (Pandemis cerasana) (common grape berry moth (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 (Phthorimaeaoperculella) (potato tuber moth), citrus leaf lyonetid (Phyllocnisitis citrella), thin moth belongs to kind of (Phyllonorycterspp.) (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 (Plutellaxylostella) (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), moth stem high genus kind at night (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 (Sparganothispilleriana), 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 (Synanthedonspp.) (root moth), Thecla basilides, Thermisia gemmatalis, casemaking clothes moth (Tineola bisselliella) (webbing clothesmoth), amyloid plaque noctuid (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 (Menopongallinea) (common hen house (common hen house)).
Orthoptera (Orthoptera) (grasshopper, locust and cricket): blackspot arna Zhong (Anabrus simplex) (katydid (Mormoncricket) rubs), 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 wingedkatydid)), Pterophylla belongs to kind of (Pterophylla spp.) (katydid), chistocerca gregaria, fork-tail katydid (Scudderiafurcata) (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), west flower thrips (Frankliniellaoccidentalis) (western flower thrips), Frankliniella shultzei, Williams flower thrips (Frankliniellawilliamsi) (corn thrips (corn thrip)), greenhouse thrips (IIeliothrips haemorrhaidalis) (greenhouse thrip), Riphiphorothrips cruentatus, hard Thrips kind (Scirtothrips spp), balloonflower root thrips (Scirtothrips cirri) (citrusthrip), tea golden thistle horse (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 ofhoneybee)), Tyroglyphus kind (Acarus spp.) (food mites), Acarus siro (Acarus siro) (paddy mite (grainmite)), 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 thorn goitre mite (Aculus schlechtendali) (apple thorn goitre mite (apple rust mite)), lone star tick (Amblyommaamcricanum) (lone star tick), Boophilus kind (Boophilus spp.) (tick), avette short hairs tick (Brevipalpusobovatus) (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 (Dermacentorvariabilis) (american dog tick), dermatophagoides pteronyssinus (Dermatophagoides pteronyssinus) (house dust mite), Eotetranychus kind (Eotetranycus spp.), carpinus turczaninowii beginning tetranychid (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.), tangerine Panonychus citri (Panonychus cirri) (orange spider (citrus red mite)), panonychus ulmi (Panonychus ulmi) (European red spider (European red mite)), tangerine wrinkle leaf thorn goitre (Phyllocoptruta oleivora) (citrusrust 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 (bulbmite)), 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.) (rootnematodes), tie Turbatrix kind (Hoplolaimus spp.) (lance nematodes), Meloidogyne kind (Meloidogynespp.) (root knot nematode), Meloidogyne incognita ((Meloidogyne incognita) (root knot nematode), Onchocerca caecutiens (Onchocercavolvulus) (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 (Rotylenchusreniformis) (kidney-shaped nematode).
Symphyla (comprehensive insects): kahikatea worm (Scutigerella immaculata).
Especially, to black peach aphid, small cabbage moth, mythimna separata, carmine spider mite, compared with still thering is good prevention effect under low dosage.
Due to its positive characteristic, above-claimed cpd can be advantageously used in protection agricultural and important crop, domestic animal and the breeding stock of horticulture, and the environment that often goes of the mankind avoids germ, insect and do harm to the injury of mite.
For obtaining ideal effect, the consumption of compound changes because of various factors, for example the formulation of the type of the crop of compound used therefor, pre-protection, harmful organism, gradient of infection, weather condition, application method, employing.
The compound dosage that per hectare is 10 grams-5 kilograms can provide sufficient control.
The present invention also comprises sterilization, the insecticide acaricide composition using compound of Formula I as active ingredient.In this sterilization, insecticide acaricide composition, the weight percentage of active ingredient is between 0.5-99%.In this sterilization, insecticide acaricide composition, also comprise acceptable carrier in agricultural, forestry, health.
Composition of the present invention can preparation form use.Compound of Formula I is as solubilization of active ingredient or be scattered in carrier or be mixed with preparation to be easier to disperse while using as sterilization, desinsection.For example: 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 can add when needed suitable tensio-active agent.
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.Conventionally the comparatively suitable significant quantity of selecting is 10 grams to 1000 grams of per hectares, and preferably significant quantity is 20 grams to 500 grams of per hectares.
For some application, for example in agricultural, can in sterilization of the present invention, insecticide acaricide composition, add one or more other sterilant, insecticidal/acaricidal agent, weedicide, plant-growth regulator or fertilizer etc., can produce thus additional advantage and effect.
Should be clear and definite, in claim limited range of the present invention, can carry out various conversion and change.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention only limit to absolutely not these examples (except as otherwise indicate outside, raw materials used all have commercially available).
Synthetic example
Embodiment 1: intermediate 4, the preparation of the chloro-6-methylpyrimidine of 5-bis-
1) preparation of the chloro-6-methylpyrimidine of 4-hydroxyl-5-
Under stirring at room temperature to 11.30g(0.11mol) slowly drip 8.80g(0.16mol in the 50ml methanol solution of FORMAMIDINE ACETATE) methanol solution of sodium methylate, drip a 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 monitors after completion of the reaction, remove solvent under reduced pressure, adjust pH=5 ~ 6 with hydrochloric acid, suction filtration obtains orange/yellow solid, (3 × 50ml) ethyl acetate extraction for water, 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%, 181 ~ 184 ℃ of fusing points.
2) 4, the preparation of the chloro-6-methylpyrimidine of 5-bis-
By 14.5g(0.1mol) the chloro-6-methylpyrimidine of 4-hydroxyl-5-is dissolved in 50ml toluene solution, under stirring, in anti-bottle, splashes into 50ml phosphorus oxychloride, drips complete temperature rising reflux reaction 5-7 hour, and TLC monitors after completion of the reaction.Remove toluene and excessive phosphorus oxychloride under reduced pressure, under stirring, by reactant impouring frozen water, (3 × 50ml) ethyl acetate extraction for water, merges organic phase, anhydrous magnesium sulfate drying, filtration, precipitation.Resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃), and volume ratio is 1:5) separates 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 benzenes, 13.3g(0.1mol) p-hydroxybenzylcyanide and 27.60g(0.2mol) salt of wormwood adds 150ml N, in dinethylformamide, under stirring, be heated to reflux, reaction is spent the night, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of 300ml ethyl acetate, organic phase is used 5% aqueous sodium hydroxide solution successively, the each 50ml washing of saturated aqueous common salt, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃) to resistates column chromatography after precipitation, volume ratio is 1:4) white solid 14.55g, yield 46.2%, 66.2 ℃ of fusing points.
2) preparation of 4-(2-chloro-trifluoromethyl phenoxy) phenylethylamine hydrochloride
Under room temperature, by 3.12g(0.01mol) mixture of intermediate 4-(2-chloro-trifluoromethyl phenoxy) benzyl cyanide, Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml composition reacts 3 hours under high-pressure hydrogenation condition.TLC monitors after completion of the reaction, and filtering Raney nickel, removes solvent under reduced pressure and obtain viscous liquid.In viscous liquid, add 15ml ethyl acetate, stirring at room temperature, drips 5ml concentrated hydrochloric acid, stirs afterwards 30min, occurs white solid.Filter to obtain white solid 3.45g, yield 97.9%, 155.7 ℃ of fusing points.
Embodiment 3: the preparation of intermediate 4-(the chloro-4-nitrophenoxy of 2,6-bis-) phenylethylamine hydrochloride
1) preparation of N-Boc-4-hydroxyphenethylamine
By 11.3g(0.1mol) 4-hydroxyphenethylamine is dissolved in 80ml tetrahydrofuran (THF), add successively 10.08g(0.12mol) sodium bicarbonate, 50ml water, under stirring at room temperature, drip 21.80g(0.1mol) tert-Butyl dicarbonate, drip and finish, continue reaction 4-10 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃) to resistates column chromatography after precipitation, volume ratio is 1:3) 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, the chloro-4-fluorine of 5-bis-nitro methylbenzene adds in 50ml butanone, add 2.76g(0.02mol) salt of wormwood, under stirring, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃) to resistates column chromatography after precipitation, volume ratio is 1:4) white solid 3.73g, yield 87.3%, fusing point 149-151 ℃.
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 monitors after completion of the reaction, removes solvent under reduced pressure, adds the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, precipitation obtains 3.03g white solid, yield 92.8%, fusing point 107-109 ℃.
Embodiment 4: the preparation of intermediate 4-(4-4-trifluoromethylphenopendant) phenylethylamine hydrochloride
1) preparation of N-Boc-4-(4-4-trifluoromethylphenopendant) phenylethylamine
By 4.56g(0.024mol) trifluoromethyl phenylo boric acid is added in 50ml methylene dichloride, under stirring at room temperature, add successively 4A molecular sieve powder, the 3.82g(0.021mol of porphyrize) Salicylaldoxime, 10.1g(0.1mol) triethylamine, 7.9g(0.1mol) pyridine, reaction is spent the night.TLC monitors after completion of the reaction, filter and remove under reduced pressure solvent, add the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃) to resistates column chromatography after precipitation, volume ratio is 1:4) white solid 5.95g, yield 65.1%.
2) preparation of 4-(4-4-trifluoromethylphenopendant) phenylethylamine hydrochloride
By 3.81g(0.01mol) N-Boc-4-(4-trifluoromethyl) phenylethylamine adds in 50ml ethyl acetate, drips 12ml concentrated hydrochloric acid under stirring at room temperature, continue to stir within 4-5 hour, to produce white solid.TLC monitors after completion of the reaction, removes solvent under reduced pressure, adds (3 × 50ml) ethyl acetate stirring at room temperature 30min, filters to obtain 2.92g white solid, yield 91.9%.
Embodiment 5: the preparation of compound 69
By 1.63g(0.01mol) 4, the chloro-6-methylpyrimidine of 5-bis-and 3.18g(0.01mol) 4-(4-4-trifluoromethylphenopendant) phenylethylamine hydrochloride adds in 50ml toluene, and stirring at room temperature is to dissolving completely.Add 4.45g(0.022mol) triethylamine, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, removes solvent under reduced pressure, adds the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, resistates column chromatography after precipitation (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃), 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
By 1.63g(0.01mol) 4, the chloro-6-methylpyrimidine of 5-bis-and 3.26g(0.01mol) 4-(the chloro-4-nitrophenoxy of 2,6-bis-) phenylethylamine hydrochloride adds in 50ml toluene, and stirring at room temperature is to dissolving completely.Add 4.45g(0.022mol) triethylamine, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, removes solvent under reduced pressure, add the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, resistates column chromatography after precipitation (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃), and volume ratio is 1:2) obtains reddish-brown solid 3.23g, yield 71.2%, fusing point 118-120 ℃.
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-(as above embodiment 1 of preparation method's reference, difference is that starting raw material 2-chloroacetyl acetacetic ester is replaced with to 2-chlorine Propionylacetic acid ethyl ester) and 2.84g(0.01mol) 4-(4-chlorophenoxy) phenylethylamine hydrochloride (preparation method is with reference to as above embodiment 4, difference is that starting raw material is replaced with chlorobenzene boric acid trifluoromethyl phenylo boric acid) add in 50ml toluene, under stirring at room temperature, add 4.45g(0.022mol) triethylamine, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃) to resistates column chromatography after precipitation, volume ratio is 1:2) reddish-brown solid 3.16g, yield 81.6%, 84.7 ℃ of fusing points.
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) phenylethylamine hydrochloride (as above embodiment 4 of preparation method's reference, difference is that starting raw material is replaced with to 3 to trifluoromethyl phenylo boric 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 reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, removes solvent under reduced pressure, adds the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, resistates column chromatography after precipitation (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃), 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
By 1.77g(0.01mol) 4, the chloro-6-ethyl-pyrimidine of 5-bis-and 3.18g(0.01mol) 4-(4-4-trifluoromethylphenopendant) phenylethylamine hydrochloride adds in 50ml toluene, and stirring at room temperature is to dissolving completely.Add 4.45g(0.022mol) triethylamine, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, removes solvent under reduced pressure, add the extraction of (3 × 50ml) ethyl acetate, saturated aqueous common salt 50ml washing for organic phase, resistates column chromatography after precipitation (eluent is ethyl acetate and sherwood oil (boiling range 60-90 ℃), and volume ratio is 1:2) obtains white solid 3.15g, yield 74.8%, 52.6 ℃ of fusing points.
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 is to terminal, remove solvent under reduced pressure, remaining for brown solid ethyl acetate (3 × 10mL) wash to obtain white solid 0.36g, yield 78.1%, 120.5 ℃ of fusing points.
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 with reference to above embodiment preparation.
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 ℃.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 ℃.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 ℃.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 ℃.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: 101.0 ℃ of fusing points.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 is except CK1 to the CK21(known compound described in background parts), also synthesize following CK22-CK64 in contrast with reference to prior art file:
Table 48 control compound
Embodiment 11: fungicidal activity is measured
The multiple fungal disease of plant is carried out to Antifungal Activity in Vitro or live body protection effect test with the compounds of this invention sample.Fungicidal activity measurement result is shown in following embodiment.
(1) in vitro fungicidal activity is measured
Measuring method is as follows: adopt high-throughput screening method, by applicable solvent testing compound sample for (kind of solvent is as acetone, methyl alcohol, DMF etc., and according to it dissolving power to sample and select) dissolving, be mixed with desired concn liquid to be measured.Under ultra-clean Working environment, liquid to be measured is joined in the micropore of 96 well culture plates, then pathogenic bacteria propagulum suspension is added wherein, culture plate after treatment is placed in constant incubator to be cultivated.After 24 hours, investigate, when investigation, estimate pathogenic bacteria propagulum 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, the compound to the inhibiting rate of rice blast more than 80% has: 19,25,53,69,165,274,347 etc., and wherein 53,165,274 inhibiting rate is 100%; Control compound CK3, CK5, CK6, CK7, CK10, CK11, CK12, CK19, CK21 to the inhibiting rate of rice blast be 0, CK4, CK8, CK9, CK14, CK18 is 50% to the inhibiting rate of rice blast;
Under 8.3ppm dosage, the compound to the inhibiting rate of rice blast more than 80% has: 53,165,274 etc., and wherein 53,165 inhibiting rate is 100%; Control compound CK1, CK20 are that 0, CK15 is 50% to the inhibiting rate of rice blast to the inhibiting rate of rice blast;
Under 2.8ppm dosage, the compound to the inhibiting rate of rice blast more than 80% has: 53,165,274 etc., and wherein 53,165 inhibiting rate is 100%; Control compound CK15 is 0 to the inhibiting rate of rice blast;
Under 0.9ppm dosage, the inhibiting rate of 53 and 165 pairs of rice blast of compound is 100%;
Under 0.3ppm dosage, the inhibiting rate of 53 and 165 pairs of rice blast of compound is 100%;
Under 0.1ppm dosage, compound 165 is 100% to the inhibiting rate of rice blast;
Under 0.03ppm dosage, compound 165 is 100% to the inhibiting rate of rice blast.
Inhibiting rate to botrytis cinerea pers:
Under 25ppm dosage, the compound of inhibiting rate more than 80% has: 69,303,347 etc., and wherein 303 inhibiting rate is 100%; Control compound CK1, CK2, CK3, CK4, CK5, CK6, CK7, CK8, CK11, CK16, CK17, CK18, CK19, CK20, CK21 are that 0, CK9, CK10 are 50% to the inhibiting rate of gray mold to the inhibiting rate of gray mold.
(2) live body prolection is measured
Measuring method is as follows: adopt the potted plant measuring method of live body, by a small amount of solvent for testing compound sample, (kind of solvent is as acetone, methyl alcohol, DMF etc., and the dissolving power according to it to sample and selecting, the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05) dissolve, with the water dilution that contains 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 potted plant seedling of standard at warm indoor cultivation), after 24 hours, carry out disease inoculation.According to disease feature, will need be placed in phytotron after the disease plant inoculating cultivated of temperature control moisturizing and cultivate, after disease completes and infects, move into hot-house culture, will not need disease plant that moisturizing cultivates directly at warm indoor inoculation and cultivate.After contrasting abundant morbidity, (be generally week age) and carry 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, compound to cucumber downy mildew preventive effect more than 80% has: 25,69,154,235,236,254,274,297,303,347,432,10018 etc., and wherein 25,69,154,236,254,297,303,347,432 preventive effects are 100%;
Under 100ppm dosage, the compound to cucumber downy mildew preventive effect more than 80% has: 25,69,236,297,303,347 etc., and wherein 236 and 297 preventive effects are 100%;
Under 50ppm dosage, the compound to cucumber downy mildew preventive effect more than 80% has: 25,236,297 etc., and wherein 236 and 297 preventive effects are 100%;
Under 25ppm dosage, the compound to cucumber downy mildew preventive effect more than 80% has: 25,236,297 etc., and wherein 236 and 297 preventive effects are 100%;
Under 12.5ppm dosage, compound 297 is 100% to cucumber downy mildew preventive effect;
Under 6.25ppm dosage, compound 297 is 100% to cucumber downy mildew preventive effect;
Under 3.125ppm dosage, compound 297 is 98% to cucumber downy mildew preventive effect.
Live body prolection to wheat powdery mildew:
Under 400ppm dosage, the compound to wheat powdery mildew preventive effect more than 80% has: 19,25,53,69,154,297,303,347,432,10018 etc., and wherein 19,25,69,154,297,303,347,432,10018 preventive effects are 100%;
Under 100ppm dosage, the compound to wheat powdery mildew preventive effect more than 80% has: 19,25,154,297,303,347,432,10018 etc., and wherein 154,297,303,347,432,10018 preventive effects are 100%;
Under 25ppm dosage, the compound to wheat powdery mildew preventive effect more than 80% has: 19,297,303,347,432,10018 etc., and wherein 297,303,347,432,10018 preventive effects are 100%;
Under 6.25ppm dosage, the compound to wheat powdery mildew preventive effect more than 80% has: 19,297,303,432,10018, and wherein 432 and 10018 preventive effects are 100%;
Under 1.6ppm dosage, the preventive effect of 303,432 pairs of wheat powdery mildews of compound is 80%;
Live body prolection to corn rust:
Under 400ppm dosage, compound to corn rust preventive effect more than 80% has: 19,25,53,69,154,165,236,254,297,303,347,432,10018 etc., and wherein 19,53,69,154,165,297,303,347,432,10018 preventive effects are 100%;
Under 100ppm dosage, the compound to corn rust preventive effect more than 80% has: 19,69,154,165,297,303,347,432,10018 etc., and wherein 69,154,297,303,347,432 preventive effects are 100%;
Under 25ppm dosage, the compound to corn rust preventive effect more than 80% has: 69,154,297,303,347,432 etc., and wherein 69,154,303,432 preventive effects are 100%;
Under 6.25ppm dosage, the compound to corn rust preventive effect more than 80% has: 154,297,303,347,432 etc., and wherein 154,303,432 preventive effects are 100%;
Under 1.6ppm dosage, compound 303 is 80% to the preventive effect of wheat powdery mildew.
(3) test result of part of compounds and contrast medicament
Carry out part of compounds and the active simultaneous test that contrasts medicament, during test result is shown in Table 49-table 51(" ///" represent not test).
The live body prolection of table 49 to cucumber downy mildew
The live body prolection of table 50 to wheat powdery mildew
The live body prolection of table 51 to corn rust
Embodiment 12: pesticide and miticide actility is measured
Several insects are carried out to insecticidal activity assay test with the compounds of this invention.Measuring method is as follows:
After the mixed solvent of acetone/methanol for testing compound (1:1) dissolves, with containing 0.1%(wt) water of tween 80 is diluted to required concentration.
Take small cabbage moth, mythimna separata, black peach aphid, carmine spider mite as target, adopt airbrush spray method to carry out insecticidal activity assay.
(1), kill the determination of activity of small cabbage moth
Measuring method: cabbage leaves is broken into the leaf dish of diameter 2cm with punch tool, the pressure that airbrush spraying is processed is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf dish pros and cons spraying, spouting liquid is 0.5ml.After drying in the shade, every processing access tries worm 10 2 ages, and every processing repeats for 3 times.After processing, put into 25 ℃, relative humidity 60～70% observation indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
Partial test result to small cabbage moth is as follows:
Under 600ppm dosage, the compound to the lethality rate of small cabbage moth more than 80% has 19,154,274,297,303,347,432,10018 etc., and wherein 19,154,297,347 and 10018 lethality rate is 100%;
Under 100ppm dosage, the lethality rate of 19 and 10018 pairs of small cabbage moths of compound is 100%.
(2), kill the determination of activity of mythimna separata
Measuring method: maize leaf is cut into the leaf section of long 2cm, the pressure that airbrush spraying is processed is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf section pros and cons spraying, spouting liquid is 0.5ml.After drying in the shade, every processing access tries worm 10 2 ages, and every processing repeats for 3 times.After processing, put into 25 ℃, relative humidity 60～70% observation indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
Partial test result to mythimna separata is as follows:
Under 600ppm dosage, the compound to the lethality rate of mythimna separata more than 80% has 19,69,297,303,347,432,10018 etc., wherein 19,69,297,347,10018 lethality rate be 100%;
Under 100ppm dosage, the compound to the lethality rate of mythimna separata more than 80% has 69,297,10018 etc.
(3), kill the determination of activity of black peach aphid
Measuring method: cut-off footpath 6cm culture dish, covers one deck filter paper, and drips appropriate tap water moisturizing at the bottom of ware.Clip suitable size (diameter 3cm) and the long cabbage leaves that has 15～30 aphids from the cabbage plant of cultivation black peach aphid, the aphid of removal alatae and face of blade, blade back is upwards placed in culture dish.The pressure that airbrush spraying is processed is 10psi (being roughly equal to 0.7kg/cm2), and spouting liquid is 0.5ml, and every processing repeats for 3 times.After processing, put into 25 ℃, relative humidity 60～70% observation indoor cultivation, 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, compound to the lethality rate of black peach aphid more than 80% has 19,25,69,154,297,303,347,432,443,10018 etc., and wherein 19,69,154,297,303,347,432,443,10018 lethality rate is 100%;
Under 10ppm dosage, the lethality rate of 19,69,297,347,10018 pairs of black peach aphids of compound is 100%;
Under 5ppm dosage, the lethality rate of 69,297,347 pairs of black peach aphids of compound is 100%, and compound 10018 is 96% to the lethality rate of black peach aphid;
Under 2.5ppm dosage, the compound to the lethality rate of black peach aphid more than 80% has 69,297,347,10018 etc., and wherein 297 and 347 lethality rate is 100%;
Under 1.25ppm dosage, the compound to the lethality rate of black peach aphid more than 80% has 297,347 etc.
(4), kill the determination of activity of carmine spider mite
Measuring method: get two true leaf Kidney bean seedlings, connect carmine spider mite and become mite and investigate after radix, carry out whole strain processing with airbrush atomizer, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5ml.Every processing repeats for 3 times, processes and is placed on standard observation ward, and 72 hours " Invest, Then Investigate " survival mite numbers, calculate mortality ratio.
Partial test result to carmine spider mite is as follows:
Under 600ppm dosage, to the lethality rate of carmine spider mite more than 80%, have 19,69,154,165,297,303,347,432,443,10018 etc., wherein 19,69,154,297,303,347,432,443,10018 lethality rate be 100%;
Under 100ppm dosage, the lethality rate of 19,69,154,297,347,432,443,10018 pairs of carmine spider mite of compound is 100%;
Under 10ppm dosage, to the lethality rate of carmine spider mite more than 80%, have 69,347,443,10018 etc., wherein 347 and 10018 lethality rate be 100%;
Under 5ppm dosage, compound 10018 is 100% to the lethality rate of carmine spider mite, and compound 347 is 90% to the lethality rate of carmine spider mite;
Under 2.5ppm dosage, compound 10018 is 87% to the lethality rate of carmine spider mite, and compound 347 is 75% to the lethality rate of carmine spider mite.
(5), the test result of part of compounds and contrast medicament
Carry out part of compounds and the active simultaneous test that contrasts medicament, during test result is shown in Table 52-table 55(" ///" represent not test).
The preventive effect of table 52 to small cabbage moth
The preventive effect of table 53 to mythimna separata
The preventive effect of table 54 to black peach aphid
The preventive effect of table 55 to 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 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 0 to 4 integer; In the time that m is greater than 1, R
3can be identical 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
12alkylthio carbonyl C
1-C
12alkyl, halo C
1-C
12alkylthio carbonyl 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 0 to 5 integer; In the time that n is greater than 1, R
4can be identical or different;
R
5, R
6can be identical or different, be selected from respectively hydrogen, halogen, C
1-C
12alkyl, C
1-C
12alkoxyl group or C
3-C
12cycloalkyl; Or R
5, R
6with the carbon composition C being 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
12thiazolinyl sulfenyl, 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
12alkyl sulfonyl-amino carbonyl, C
1-C
12alkyl-carbonyl-amino alkylsulfonyl, C
3-C
12cycloalkyl oxy carbonyl, 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
12alkynyloxy group carbonyl, 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 unsubstituted or that further replaced by the following group of 1-5
1-C
6alkyl, (mixing) aryl carbonyl, (mixing) aryloxycarbonyl, (mixing) aryl C
1-C
6alkyl oxy carbonyl, (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
9can be identical or different, be selected from respectively hydrogen, C
1-C
12alkyl or halo C
1-C
12alkyl;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
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 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 0 to 4 integer; In the time that m is greater than 1, R
3can be identical 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
6alkylthio carbonyl C
1-C
6alkyl, halo C
1-C
6alkylthio carbonyl 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 0 to 5 integer; In the time that n is greater than 1, R
4can be identical or different;
R
5, R
6can be identical or different, be selected from respectively hydrogen, halogen, C
1-C
6alkyl, C
1-C
6alkoxyl group or C
3-C
6cycloalkyl; Or R
5, R
6with the carbon composition C being 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
9can be identical or different, be selected from respectively hydrogen, C
1-C
6alkyl or halo C
1-C
6alkyl;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
3. compound according to claim 2, is characterized in that: 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 0 to 4 integer; In the time that m is greater than 1, R
3can be identical 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
4alkylthio carbonyl C
1-C
4alkyl, halo C
1-C
4alkylthio carbonyl 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 0 to 5 integer; In the time that n is greater than 1, R
4can be identical or different;
R
5, R
6can be identical or different, be selected from respectively hydrogen, halogen, C
1-C
4alkyl, C
1-C
4alkoxyl group or C
3-C
6cycloalkyl; Or R
5, R
6with the carbon composition C being 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
9can be identical or different, be selected from respectively hydrogen, C
1-C
4alkyl or halo C
1-C
4alkyl;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
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-, 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 1 to 2 integer;
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 0 to 5 integer;
R
5, R
6can be identical or different, be selected from respectively 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;
R
7be selected from hydrogen;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
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-, the tertiary butyl, cyclopropyl or cyclobutyl;
R
2be selected from fluorine, chlorine or bromine;
R
3be selected from independently of one another respectively hydrogen, fluorine, chlorine or bromine; M is selected from 1 to 2 integer;
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 1 to 5 integer;
R
5, R
6can be identical or different, be selected from respectively hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy;
R
7be selected from hydrogen;
Be selected from-CH of A
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of 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 formation.
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 1 to 5 integer;
Be selected from-CH of A
2-;
Or the salt of compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or trifluoroacetic acid formation.
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-, be selected from-CH of A
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 4-chlorine, 3, the chloro-4-trifluoromethyl of 5-dichloro, 4-trifluoromethyl or 2-, be selected from-CH of A
2-;
Or the salt of above-claimed cpd and hydrochloric acid formation.
8. a compound of Formula I according to claim 1 or its salt are used as the purposes of preparing sterilant, Insecticiding-miticiding agent medicine in agricultural, forestry or health field.
9. a sterilization and disinsection miticide composition, is characterized in that: contain compound of Formula I as claimed in claim 1 or its salt as active ingredient, in composition, the weight percentage of active ingredient is 0.5-99%.
10. a method of preventing and treating germ, insect evil mite, is characterized in that: the composition claimed in 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 |
| EP20184845.4A EP3760617B1 (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 |
| US14/423,953 US9770026B2 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| 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 |
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 true CN103772294A (en) | 2014-05-07 |
| CN103772294B 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485644A (en) * | 2017-09-12 | 2019-03-19 | 山东省联合农药工业有限公司 | A kind of substituted benzo isothiazole compound and preparation method thereof and purposes |
| CN114516868A (en) * | 2020-11-20 | 2022-05-20 | 湖南海利常德农药化工有限公司 | N-heteroaryl methyl difluoromethyl pyrimidinamine compound and preparation method and application thereof |
Citations (3)
| 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 |
| JPH1036355A (en) * | 1996-07-19 | 1998-02-10 | Ube Ind Ltd | Production of 4-amino-5-chloro-6-(1-fluoroehyl)pyrimidine derivative |
| US5925644A (en) * | 1996-11-15 | 1999-07-20 | Hoechst Schering Agrevo Gmbh | Substituted nitrogen heterocycles, processes for their preparation and their use as pesticides |
-
2012
- 2012-10-25 CN CN201210412091.0A patent/CN103772294B/en active Active
Patent Citations (3)
| 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 |
| JPH1036355A (en) * | 1996-07-19 | 1998-02-10 | Ube Ind Ltd | Production of 4-amino-5-chloro-6-(1-fluoroehyl)pyrimidine derivative |
| US5925644A (en) * | 1996-11-15 | 1999-07-20 | Hoechst Schering Agrevo Gmbh | Substituted nitrogen heterocycles, processes for their preparation and their use as pesticides |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485644A (en) * | 2017-09-12 | 2019-03-19 | 山东省联合农药工业有限公司 | A kind of substituted benzo isothiazole compound and preparation method thereof and purposes |
| CN109485644B (en) * | 2017-09-12 | 2020-11-10 | 山东省联合农药工业有限公司 | Substituted benzisothiazole compound and preparation method and application thereof |
| CN114516868A (en) * | 2020-11-20 | 2022-05-20 | 湖南海利常德农药化工有限公司 | N-heteroaryl methyl difluoromethyl pyrimidinamine compound and preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772294B (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105722837B (en) | Pyrazolyl pyrimidines aminated compounds and purposes | |
| CN104797575B (en) | Homopiperony lamine class compound and application thereof | |
| CN106167484A (en) | Substituted pyrazolecarboxylic compounds containing pyrimidine and its production and use | |
| CN105348298B (en) | Substituted aryl pyridine compounds and their and application thereof | |
| CN104684900B (en) | Substituted pyrimidine compound and uses thereof | |
| CN103772293B (en) | Fluorine-containing pyrimidines and purposes | |
| CN108623562A (en) | A kind of quinolinone alkaloid class compound and its preparation method and application | |
| CN109776427A (en) | Double aminated compounds of pyrimidine and application thereof | |
| CN107964007A (en) | Pyridazinone compound and its application | |
| 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 | |
| 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 | |
| CN104974136B (en) | Pyrazol acid amide compounds and application thereof | |
| CN103772294B (en) | Phenoxy pyrimidine aminated compounds and purposes | |
| CN108069973A (en) | Substitution hexa-member heterocycle class compound of the ring containing pyrimido and its preparation method and application | |
| CN105753791B (en) | Substituted uracil compound and application thereof | |
| CN103772356A (en) | Substituted aryloxy pyridine compound and use thereof | |
| CN105315296B (en) | Substitute fragrant oxy picolinate class compound and application thereof | |
| CN109485644A (en) | A kind of substituted benzo isothiazole compound and preparation method thereof and purposes | |
| CN108689928A (en) | A kind of quinoline derivatives and preparation method thereof and purposes | |
| CN106279040A (en) | Pyrimidines containing oximido and application thereof | |
| CN105732585B (en) | Replace fragrant oxy picolinate class compound and application 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 |