CN103772356B - Replace fragrant oxy picolinate compounds and uses thereof - Google Patents
Replace fragrant oxy picolinate compounds and uses thereof Download PDFInfo
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- CN103772356B CN103772356B CN201210412048.4A CN201210412048A CN103772356B CN 103772356 B CN103772356 B CN 103772356B CN 201210412048 A CN201210412048 A CN 201210412048A CN 103772356 B CN103772356 B CN 103772356B
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- 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
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Abstract
The invention discloses and replace fragrant oxy picolinate compounds, compound structure is as shown in general formula I:
Description
Technical field
The invention belongs to agricultural bactericidal, field of pesticides.Relate to fragrant oxy picolinate compounds of a kind of replacement and uses thereof particularly.
Background technology
Patent EP0370704 and JP2009161472 discloses following compound formula and particular compound (numbering in two patents is respectively compound 47 and compd A), has sterilization and insecticidal activity.Now be developed as commercialization sterilant, English popular name diflumetorim, Universal Chinese character name fluorine mepanipyrim.PesticideScience.1999,55:896-902 also disclose following particular compound (being numbered compound 5 in document), and raw result of surveying shows to have certain activity to wheat rust and barley powdery mildew.
Fluorine mepanipyrim
Patent JP11012253, JP11049759, EP0665225 disclose the preparation method of following compound (being numbered compound 7 in JP11012253), the English popular name Flufenerim of this compound, the phonetic worm amine of Universal Chinese character name.
Phonetic worm amine
Patent WO9507278 discloses the compound shown in following general formula and has certain sterilization, kills mite and/or insecticidal activity, and wherein TABLE1 the 209th row is referred to compound K C1, KC2, KC3, but reports without any biological activity;
Patent WO9404527 discloses in following compound K C4(patent and is numbered 46), be numbered 49 in KC5(patent), under 50ppm dosage, there is good insecticidal activity; Respectively under 400ppm and 100ppm dosage, there is good fungicidal activity.
Carry out online information retrieval by Scifinder, retrieve compound K C6(casNo.203734-18-3) and KC7(casNo.203734-22-9), but without concrete bibliographical information, also inactive report.
WO9728133 discloses in following general formula and particular compound KC8(patent and is numbered 26), there is sterilization, desinsection, acaricidal activity:
Patent US5227387 discloses in following general formula and particular compound KC9(patent and is numbered 81), there is eelworm-killing activity.
US5326766 discloses in following general formula and particular compound KC10(patent and is numbered 29), there is sterilization, insecticidal activity:
Patent US5925644 discloses in following general formula and particular compound KC11(patent and is numbered 447), there is desinsection, kill mite, eelworm-killing activity.
Patent EP264217, DE3786390, US4895849, US4985426, JP63225364 disclose numbering in the pyrimidine benzylamine compound general formula shown in following general formula and particular compound KC12 and KC13(EP264217 and are respectively compound 74 and compound 77), as the application of agricultural bactericidal, Insecticidal and acaricidal agent etc.
Patent EP534341 discloses in following general formula and particular compound KC14(patent and is numbered compound 98), be numbered compound 271 in KC15(patent), be numbered compound 117 in KC16(patent), there is certain sterilization, insecticidal activity.
EP0665225, JP10036355, US5498612 to report in following pyrimidinamine compound general formula and particular compound KC17, KC18 and KC19(EP0665225 numbering and are respectively compound 83, compound 87 and compound 101) preparation method, there is desinsection, sterilization, acaricidal activity.
In prior art, the compound of structure as shown in general formula I of the present invention has no report.
Summary of the invention
Modern agricultural production needs the novel pesticide continually developing out novel structure, excellent performance.The object of the present invention is to provide a kind of replacement virtue oxy picolinate compounds that just can control multiple germ, insect 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 the fragrant oxy picolinate compounds of a kind of replacement, compound structure is as shown in general formula I:
In formula:
R
1be selected from hydrogen, halogen, C
1-C
12alkyl, C
3-C
12cycloalkyl, halo C
1-C
12alkyl, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12alkynyl, C
1-C
12alkoxy C
1-C
12alkyl or halo C
1-C
12alkoxy C
1-C
12alkyl;
R
2be selected from hydrogen, halogen, cyano group, C
1-C
12alkyl, C
1-C
12alkoxyl group or halo C
1-C
12alkoxyl group;
R
3be selected from hydrogen, halogen, C
1-C
12alkyl, C
1-C
12alkoxyl group, C
1-C
12alkylthio or C
1-C
12alkyl sulphonyl;
R
4, R
5may be the same or different, be selected from hydrogen, C
1-C
12alkyl, C
3-C
12cycloalkyl, 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, aryl C that is unsubstituted or that replaced further by 1-5 following group
1-C
6alkyl or heteroaryl C
1-C
6alkyl: halogen, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group or halo C
1-C
6alkoxyl group; Or R
4, R
5c is formed with the carbon be connected
3-C
8ring;
R
6, R
7, R
8be selected from hydrogen, halogen, nitro, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
3-C
12cycloalkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12alkynyl, C
3-C
12alkene oxygen base, halo C
3-C
12alkene oxygen base, C
3-C
12alkynyloxy group, halo C
3-C
12alkynyloxy group, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy carbonyl, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkoxycarbonyl amino, C
1-C
12alkoxy C
1-C
12alkoxyl group or C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group;
R
9be selected from hydrogen, halogen, hydroxyl, cyano group, carboxyl, amino, 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
2-C
12thiazolinyl, C
2-C
12alkynyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl, halo C
1-C
12alkylthio C
1-C
12alkyl, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl amino sulfonyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, two (C
1-C
12alkyl) amino, C
1-C
12alkoxy carbonyl, CONH
2, C
1-C
12alkyl amino-carbonyl, two (C
1-C
12alkyl) aminocarboxyl, cyano group C
1-C
12alkoxyl group, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkyl amino-carbonyl C
1-C
12alkyl or two (C
1-C
12alkyl) aminocarboxyl C
1-C
12alkyl;
A is selected from NR
14, O or S;
B is selected from-CH
2-or-CH
2cH
2-;
W is selected from N or CR
10;
X is selected from N or CR
11;
Y is selected from N or CR
12;
Z is selected from N or CR
13; But W, X, Y, Z are selected from N time different;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, hydroxyl, cyano group, carboxyl, amino, nitro, C respectively
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkoxy carbonyl, CONH
2, C
1-C
12alkyl amino-carbonyl or two (C
1-C
12alkyl) aminocarboxyl;
R
14be selected from hydrogen, hydroxyl, formyl radical, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
12cycloalkyl, C
1-C
12alkylthio, C
2-C
12enylsulfanyl, C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12thiazolinyl, halo C
2-C
12alkynyl, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl, halo C
1-C
12alkylthio C
1-C
12alkyl, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl amino sulfonyl, two (C
1-C
12alkyl) amino-sulfonyl, C
1-C
12alkylsulfonyl aminocarbonyl, C
1-C
12alkyl-carbonyl-amino alkylsulfonyl, C
3-C
12cycloalkyloxycarbonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl, halo C
1-C
12alkoxy carbonyl, C
1-C
12alkyl-carbonyl C
1-C
12alkyl, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkyl amino-carbonyl, two (C
1-C
12alkyl) aminocarboxyl, C
2-C
12allyloxycarbonyl, C
2-C
12alkynyloxycar bonyl, C
1-C
12alkoxy C
1-C
12alkoxy carbonyl, C
1-C
12alkylamino sulfenyl, two (C
1-C
12alkyl) amino sulfenyl, (mixing) aryl carbonyl C that is unsubstituted or that replaced further by the following group of 1-5
1-C
6alkyl, (mixing) aryl carbonyl, (mixing) aryloxycarbonyl, (mixing) aryl C
1-C
6alkyloxycarbonyl or (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;
Or the salt of compound of Formula I.
The comparatively preferred compound of the present invention is: in general formula I
R
1be selected from hydrogen, halogen, C
1-C
8alkyl, C
3-C
8cycloalkyl, halo C
1-C
8alkyl, C
2-C
8thiazolinyl, halo C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8alkynyl, C
1-C
8alkoxy C
1-C
8alkyl or halo C
1-C
8alkoxy C
1-C
8alkyl;
R
2be selected from hydrogen, halogen, cyano group, C
1-C
8alkyl, C
1-C
8alkoxyl group or halo C
1-C
8alkoxyl group;
R
3be selected from hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
1-C
8alkylthio or C
1-C
8alkyl sulphonyl;
R
4, R
5may be the same or different, be selected from hydrogen, C
1-C
8alkyl, C
3-C
8cycloalkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8thiazolinyl, halo C
2-C
8alkynyl, C
1-C
8alkoxy C
1-C
8alkyl, aryl C that is unsubstituted or that replaced further by 1-3 following group
1-C
4alkyl or heteroaryl C
1-C
4alkyl: halogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group; Or R
4, R
5c is formed with the carbon be connected
3-C
8ring;
R
6, R
7, R
8be selected from hydrogen, halogen, nitro, cyano group, C
1-C
8alkyl, halo C
1-C
8alkyl, C
3-C
6cycloalkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
2-C
8thiazolinyl, halo C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8alkynyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy carbonyl, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
1-C
8alkoxycarbonyl amino, C
1-C
8alkoxy C
1-C
8alkoxyl group or C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group;
R
9be selected from hydrogen, halogen, hydroxyl, cyano group, carboxyl, amino, nitro, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
3-C
8cycloalkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl, C
2-C
8alkene oxygen base, halo C
2-C
8alkene oxygen base, C
2-C
8alkynyloxy group, halo C
2-C
8alkynyloxy group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl, halo C
1-C
8alkylthio C
1-C
8alkyl, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl amino sulfonyl, C
1-C
8alkylamino, halo C
1-C
8alkylamino, two (C
1-C
8alkyl) amino, C
1-C
8alkoxy carbonyl, CONH
2, C
1-C
8alkyl amino-carbonyl, two (C
1-C
8alkyl) aminocarboxyl, cyano group C
1-C
8alkoxyl group, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
1-C
8alkyl amino-carbonyl C
1-C
8alkyl or two (C
1-C
8alkyl) aminocarboxyl C
1-C
8alkyl;
A is selected from NR
14, O or S;
B is selected from-CH
2-or-CH
2cH
2-;
W is selected from N or CR
10;
X is selected from N or CR
11;
Y is selected from N or CR
12;
Z is selected from N or CR
13;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, hydroxyl, cyano group, carboxyl, amino, nitro, C respectively
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkoxy carbonyl, CONH
2, C
1-C
8alkyl amino-carbonyl or two (C
1-C
8alkyl) aminocarboxyl;
R
14be selected from hydrogen, hydroxyl, formyl radical, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
3-C
8cycloalkyl, C
1-C
8alkylthio, C
2-C
8enylsulfanyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8thiazolinyl, halo C
2-C
8alkynyl, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl, halo C
1-C
8alkylthio C
1-C
8alkyl, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl amino sulfonyl, two (C
1-C
8alkyl) amino-sulfonyl, C
1-C
8alkylsulfonyl aminocarbonyl, C
1-C
8alkyl-carbonyl-amino alkylsulfonyl, C
3-C
8cycloalkyloxycarbonyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkoxy carbonyl, halo C
1-C
8alkoxy carbonyl, C
1-C
8alkyl-carbonyl C
1-C
8alkyl, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
1-C
8alkyl amino-carbonyl, two (C
1-C
8alkyl) aminocarboxyl, C
2-C
8allyloxycarbonyl, C
2-C
8alkynyloxycar bonyl, C
1-C
8alkoxy C
1-C
8alkoxy carbonyl, C
1-C
8alkylamino sulfenyl, two (C
1-C
8alkyl) amino sulfenyl, (mixing) aryl carbonyl C that is unsubstituted or that replaced further by the following group of 1-3
1-C
6alkyl, (mixing) aryl carbonyl, (mixing) aryloxycarbonyl, (mixing) aryl C
1-C
6alkyloxycarbonyl or (mixing) aryl C
1-C
6alkyl: halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
Or the salt of compound of Formula I.
Preferred compound is further: in general formula I
R
1be selected from hydrogen, halogen, C
1-C
4alkyl, C
3-C
6cycloalkyl, halo C
1-C
4alkyl, C
2-C
4thiazolinyl, halo C
2-C
4thiazolinyl, C
2-C
4alkynyl, halo C
2-C
4alkynyl, C
1-C
4alkoxy C
1-C
4alkyl or halo C
1-C
4alkoxy C
1-C
4alkyl;
R
2be selected from halogen;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen, methyl or ethyl;
R
6, R
7, R
8may be the same or different, be selected from hydrogen, halogen, nitro, cyano group, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
2-C
4thiazolinyl, C
2-C
4alkynyl, C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkyl-carbonyl or C
1-C
4alkoxy C
1-C
4alkoxyl group;
R
9be selected from hydrogen, halogen, hydroxyl, cyano group, carboxyl, amino, 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
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
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkoxy C
1-C
4alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
1-C
4alkylthio C
1-C
4alkyl, halo C
1-C
4alkylthio C
1-C
4alkyl, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkyl amino sulfonyl, C
1-C
4alkylamino, halo C
1-C
4alkylamino, two (C
1-C
4alkyl) amino, C
1-C
4alkoxy carbonyl, CONH
2, C
1-C
4alkyl amino-carbonyl, two (C
1-C
4alkyl) aminocarboxyl, cyano group C
1-C
12alkoxyl group, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, C
1-C
4alkyl amino-carbonyl C
1-C
4alkyl or two (C
1-C
4alkyl) aminocarboxyl C
1-C
4alkyl;
A is selected from NH, O or S;
B is selected from-CH
2-or-CH
2cH
2-;
W is selected from N or CR
10;
X is selected from N or CR
11;
Y is selected from N or CR
12;
Z is selected from N or CR
13;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, hydroxyl, cyano group, carboxyl, amino, nitro, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, CONH
2, C
1-C
4alkyl amino-carbonyl or two (C
1-C
4alkyl) aminocarboxyl;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
Further preferred compound is: in general formula I
The compound of structure as shown in I-A, I-B, I-C, I-D, I-E, I-F, I-G, I-H, I-I or I-J:
R
1be selected from hydrogen, halogen, C
1-C
4alkyl, C
3-C
6cycloalkyl, halo C
1-C
4alkyl, C
2-C
4thiazolinyl, C
2-C
4alkynyl, C
1-C
4alkoxy C
1-C
4alkyl or halo C
1-C
4alkoxy C
1-C
4alkyl;
R
2be selected from halogen;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen, methyl or ethyl;
R
6, R
7, R
8may be the same or different, be selected from hydrogen, halogen, nitro, cyano group, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group or C
1-C
4alkyl-carbonyl;
R
9be selected from hydrogen, halogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
A is selected from NH, O or S;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
Or, the salt that general formula I-A, I-B, I-C, I-D, I-E, I-F, I-G, I-H, I-I or I-J compound and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
Preferred compound is further again: in general formula I-A
R
1be selected from chlorine, methyl, ethyl, CHF
2or trifluoromethyl;
R
2be selected from halogen;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen;
R
6, R
8be selected from hydrogen;
R
7be selected from hydrogen or halogen;
R
9be selected from hydrogen, halogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
A is selected from NH;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
Or, the salt that general formula I-A compound and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
In the present invention, further preferred compound is: in general formula I-A
R
1be selected from chlorine, methyl, ethyl, CHF
2or trifluoromethyl;
R
2be selected from chlorine;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen;
R
6, R
8be selected from hydrogen;
R
7be selected from hydrogen;
R
9be selected from hydrogen, chlorine, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy;
A is selected from NH;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, chlorine, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy respectively;
Or, the salt that general formula I-A compound and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
The preferred particular compound of the present invention is, in general formula I-A
R
1be selected from methyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13be selected from hydrogen, A is selected from NH; Or
R
1be selected from methyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
13be selected from hydrogen, R
12be selected from methyl, chlorine, methoxyl group or trifluoromethyl, A is selected from NH; Or
R
1be selected from ethyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
13be selected from hydrogen, R
12be selected from chlorine, trifluoromethyl or trifluoromethoxy, A is selected from NH; Or
R
1be selected from ethyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
11, R
13be selected from hydrogen, R
10, R
12be selected from chlorine, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13be selected from hydrogen, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
13be selected from hydrogen, R
12be selected from chlorine or trifluoromethyl, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
12, R
13be selected from hydrogen, R
11be selected from trifluoromethyl, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
11, R
13be selected from hydrogen, R
10, R
12be selected from chlorine, A is selected from NH;
Or, the salt that above-claimed cpd and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
In the definition of the compound of Formula I provided, collect the following substituting group of term general proxy used: halogen: refer to fluorine, chlorine, bromine or iodine above.Alkyl: straight or branched alkyl, such as methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl.Cycloalkyl: substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl.Substituting group is as methyl, halogen etc.Haloalkyl: straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely replace by halogen atom, such as, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc.Alkoxyl group: straight or branched alkyl, is connected in structure through Sauerstoffatom key.Halogenated alkoxy: straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely replace by halogen atom.Such as, chlorine methoxyl group, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc.Alkylthio: straight or branched alkyl, is connected in structure through sulphur atom key.Thiazolinyl: straight or branched alkene class, such as vinyl, 1-propenyl, 2-propenyl and different butenyls, pentenyl and hexenyl isomers.Thiazolinyl also comprises polyenoid class, as 1,2-propadiene base and 2,4-hexadienyl.Haloalkenyl group: straight or branched alkene class, the hydrogen atom on these thiazolinyls can partly or entirely replace by halogen atom.Alkynyl: straight or branched alkynes class, such as ethynyl, 1-proyl, 2-propynyl and different butynyl, pentynyl and hexynyl isomers.Alkynyl also comprises the group be made up of multiple triple bond, as 2,5-hexadiyne base.Halo alkynyl: straight or branched alkynes class, the hydrogen atom on these alkynyls can partly or entirely replace by halogen atom.Alkene oxygen base: straight or branched alkene class, is connected in structure through Sauerstoffatom key.Enylsulfanyl: straight or branched alkene class, is connected in structure through sulphur atom key.As CH
2=CHCH
2s-.Haloalkene oxygen base: straight or branched alkene oxygen base, the hydrogen atom on these alkene oxygen bases can partly or entirely replace by halogen atom.Alkynyloxy group: straight or branched alkynes class, is connected in structure through Sauerstoffatom key.Halo alkynyloxy group: straight or branched alkynyloxy group, the hydrogen atom on these alkynyloxy groups can partly or entirely replace by halogen atom.Allyloxycarbonyl: as CH
2=CHCH
2oCO-etc.Alkynyloxycar bonyl: as CH ≡ CCH
2oCO-etc.Alkylamino: straight or branched alkyl, is connected in structure through nitrogen-atoms key.Cyanoalkyl is amino: the hydrogen atom on the alkyl of alkylamino can partly or entirely replace by cyano group, such as, CNCH
2nH-, CNCH
2cH
2nH-etc.Alkyl sulphinyl: straight or branched alkyl is connected in structure, as methylsulfinyl through sulfinyl (-SO-).Alkylsulfinyl: straight or branched alkyl sulphinyl, the hydrogen atom on its alkyl can partly or entirely replace by halogen atom.Alkyl sulphonyl: straight or branched alkyl is through alkylsulfonyl (-SO
2-) be connected in structure, as methyl sulphonyl.Halogenated alkyl sulfonyl: straight or branched alkyl sulphonyl, the hydrogen atom on its alkyl can partly or entirely replace by halogen atom.Alkyl-carbonyl: alkyl is connected in structure, as CH through carbonyl
3cO-, CH
3cH
2cO-.Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can partly or entirely replace by halogen atom, as CF
3cO-.Alkyl-carbonyl-amino: as CH
3cONH-, CH
3cH
2nHCONH-.Alkyl sulphonyl oxygen base: alkyl-S (O)
2-O-.Alkoxy carbonyl: alkyl-O-CO-, as CH
3oCO-, C
2h
5oCO-.Halo alkoxy carbonyl: the hydrogen atom on the alkyl of alkoxy carbonyl can partly or entirely replace by halogen atom, as ClCH
2cH
2oCO-, CF
3cH
2oCO-etc.Alkoxy carbonyl alkyl: alkoxy carbonyl-alkyl-, such as CH
3oCOCH
2-.Alkoxycarbonyl amino: alkyl-O-CO-NH-.Alkoxyalkyl: alkyl-O-alkyl-, such as CH
3oCH
2-.Halogenated alkoxy alkyl: the hydrogen atom on the alkyl of alkoxyalkyl can partly or entirely replace by halogen atom.As ClCH
2cH
2oCH
2-.Alkylthio alkyl: alkyl-S-alkyl-, such as CH
3sCH
2-.Haloalkylthioalkyl: the hydrogen atom on the alkyl of alkylthio alkyl can partly or entirely replace by halogen atom, as ClCH
2cH
2sCH
2-, CF
3cH
2sCH
2-etc.Alkyl amino sulfonyl: alkyl-NH-SO
2-.Dialkyl amino sulfonyl: (alkyl)
2-N-SO
2-.Alkylsulfonyl aminocarbonyl: alkyl-SO
2-NH-CO-.Alkyl-carbonyl-amino alkylsulfonyl: alkyl-CO-NH-SO
2-.Cycloalkyloxycarbonyl: as ring propoxycarbonyl, cyclohexyloxy carbonyl etc.Alkylcarbonylalkyl: alkyl-CO-alkyl-.Alkyl amino-carbonyl: alkyl-NH-CO-, such as CH
3nHCO-, (CH
3)
2nCO-.Dialkyl amino carbonyl: (alkyl)
2-NH-CO-, such as (CH
3)
2-N-CO-, (C
2h
5)
2-N-CO-.Alkoxyalkoxycarbonyl: as CH
3oCH
2cH
2oCO-etc.Alkylamino sulfenyl: as CH
3nHS-, C
2h
5nHS-.Dialkyl amido sulfenyl: as (CH
3)
2nS-, (C
2h
5)
2nS-.Alkylsulfinylalkyl: as CH
3sOCH
2-.Alkylsulfonylalkyl: as CH
3sO
2cH
2-.Hydroxyalkyl: as HOCH
2-.Alkylcarbonyloxyalkyl: as CH
3cOOCH
2-.Aryl moiety in (mixing) aryl alkyl carbonyl, (mixing) aryl carbonyl, (mixing) aryloxycarbonyl, (mixing) arylalkyl oxygen base carbonyl, (mixing) arylalkyl comprises phenyl or naphthyl etc.Heteroaryl is containing the heteroatomic five-ring of one or more N, O, S or six-ring.Such as furyl, pyrazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl etc.(mixing) aryl alkyl carbonyl: as PhCOCH
2-.(mixing) aryl carbonyl: as benzoyl, 4-chlorobenzene formacyl, picolinoyl, pyrimidine formyl radical, pyrazoyl etc.(mixing) aryloxycarbonyl: as phenyloxycarbonyl, 4-cHorophenoxycarbonyl, 4-nitrophenoxy carbonyl, naphthoxycarbonyl, pyridyloxy carbonyl, 2-pyrimidinyl oxy carbonyl etc.(mixing) arylalkyl oxygen base carbonyl: as benzyloxycarbonyl, 4-chlorobenzyl oxygen base carbonyl, 4-trifluoromethyl benzyl oxygen base carbonyl, picolyl oxygen base carbonyl etc.(mixing) arylalkyl: as phenmethyl, styroyl, to chlorophenylmethyl,
deng.
Table 1 lists R in general formula I respectively to table 4
1, R
2, R
3, R
4, R
5the concrete substituting group of part, but they are not limited only to these substituting groups, and in general formula I, other substituting groups are as previously mentioned.
Table 1R
1substituting group
Table 2R
2substituting group
| R 2 | R 2 | R 2 | R 2 |
| H | NO 2 | t-C 4H 9 | OC 4H 9-i |
| F | CH 3 | OCH 3 | OC 4H 9-t |
| Cl | C 2H 5 | OC 2H 5 | OCH 2F |
| Br | n-C 3H 7 | OC 3H 7-n | OCHF 2 |
| I | i-C 3H 7 | OC 3H 7-i | OCF 3 |
| CN | n-C 4H 9 | OC 4H 9-n | OCH 2CF 3 |
Table 3R
3substituting group
Table 4R
4(R
5) substituting group
Part of compounds of the present invention can illustrate by the particular compound listed in table 5-table 98, but does not limit the present invention.In general formula compound I-A, I-B, I-C, I-D, I-E, I-F, I-G, I-H of relating in table, R
6=R
8=H.
In general formula I-A,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
10, R
11, R
12, R
13substituting group, in table 5, representation compound is numbered 1-180.
Table 5
| Numbering | R 9 | R 10 | R 11 | R 12 | R 13 |
| 1 | H | H | H | H | H |
| 2 | H | F | H | H | H |
| 3 | H | H | F | H | H |
| 4 | H | H | H | F | H |
| 5 | H | Cl | H | H | H |
| 6 | H | H | Cl | H | H |
| 7 | H | H | H | Cl | H |
| 8 | H | Br | H | H | H |
| 9 | H | H | Br | H | H |
| 10 | H | H | H | Br | H |
| 11 | H | I | H | H | H |
| 12 | H | H | I | H | H |
| 13 | H | H | H | I | H |
| 14 | H | CH 3 | H | H | H |
| 15 | H | H | CH 3 | H | H |
| 16 | H | H | H | CH 3 | H |
| 17 | H | OCH 3 | H | H | H |
| 18 | H | H | OCH 3 | H | H |
| 19 | H | H | H | OCH 3 | H |
| 20 | H | CF 3 | H | H | H |
| 21 | H | H | CF 3 | H | H |
| 22 | H | H | H | CF 3 | H |
| 23 | H | OCF 3 | H | H | H |
| 24 | H | H | OCF 3 | H | H |
| 25 | H | H | H | OCF 3 | H |
| 26 | H | NO 2 | H | H | H |
| 27 | H | H | NO 2 | H | H |
| 28 | H | H | H | NO 2 | H |
| 29 | H | CN | H | H | H |
| 30 | H | H | CN | H | H |
| 31 | H | H | H | CN | H |
| 32 | H | CH(CH 3) 2 | H | H | H |
| 33 | H | H | CH(CH 3) 2 | H | H |
| 34 | H | H | H | CH(CH 3) 2 | H |
| 35 | H | H | H | t-Bu | H |
| 36 | H | SCH 3 | H | H | H |
| 37 | H | H | SCH 3 | H | H |
| 38 | H | H | H | SCH 3 | H |
| 39 | H | SCF 3 | H | H | H |
| 40 | H | H | SCF 3 | H | H |
| 41 | H | H | H | SCF 3 | H |
| 42 | H | COCH 3 | H | H | H |
| 43 | H | H | COCH 3 | H | H |
| 44 | H | H | H | COCH 3 | H |
| 45 | H | SOCH 3 | H | H | H |
| 46 | H | H | SOCH 3 | H | H |
| 47 | H | H | H | SOCH 3 | H |
| 48 | H | SO 2CH 3 | H | H | H |
| 49 | H | H | SO 2CH 3 | H | H |
| 50 | H | H | H | SO 2CH 3 | H |
| 51 | H | OCHF 2 | H | H | H |
| 52 | H | H | OCHF 2 | H | H |
| 53 | H | H | H | OCHF 2 | H |
| 54 | H | CO 2CH 3 | H | H | H |
| 55 | H | H | CO 2CH 3 | H | H |
| 56 | H | H | H | CO 2CH 3 | H |
| 57 | H | N(CH 3) 2 | H | H | H |
| 58 | H | H | N(CH 3) 2 | H | H |
| 59 | H | H | H | N(CH 3) 2 | H |
| 60 | H | N(C 2H 5) 2 | H | H | H |
| 61 | H | H | N(C 2H 5) 2 | H | H |
| 62 | H | H | H | N(C 2H 5) 2 | H |
| 63 | H | NHCOCH 3 | H | H | H |
| 64 | H | H | NHCOCH 3 | H | H |
| 65 | H | H | H | NHCOCH 3 | H |
| 66 | H | NHSO 2CH 3 | H | H | H |
| 67 | H | H | NHSO 2CH 3 | H | H |
| 68 | H | H | H | NHSO 2CH 3 | H |
| 69 | H | OCH 2CH=CH 2 | H | H | H |
| 70 | H | H | OCH 2CH=CH 2 | H | H |
| 71 | H | H | H | OCH 2CH=CH 2 | H |
| 72 | H | OCH 2C≡CH | H | H | H |
| 73 | H | H | OCH 2C≡CH | H | H |
| 74 | H | H | H | OCH 2C≡CH | H |
| 75 | H | F | F | H | H |
| 76 | H | F | H | F | H |
| 77 | F | F | H | H | H |
| 78 | H | F | H | H | F |
| 79 | H | H | F | F | H |
| 80 | F | H | F | H | H |
| 81 | H | Cl | Cl | H | H |
| 82 | H | Cl | H | Cl | H |
| 83 | Cl | Cl | H | H | H |
| 84 | H | Cl | H | H | Cl |
| 85 | H | H | Cl | Cl | H |
| 86 | Cl | H | Cl | H | H |
| 87 | H | NO 2 | H | NO 2 | H |
| 88 | NO 2 | NO 2 | H | H | H |
| 89 | H | NO 2 | H | H | NO 2 |
| 90 | NO 2 | H | NO 2 | H | H |
| 91 | H | CN | H | CN | H |
| 92 | CN | CN | H | H | H |
| 93 | H | CN | H | H | CN |
| 94 | CN | H | CN | H | H |
| 95 | H | CH 3 | CH 3 | H | H |
| 96 | H | CH 3 | H | CH 3 | H |
| 97 | CH 3 | CH 3 | H | H | H |
| 98 | H | CH 3 | H | H | CH 3 |
| 99 | H | H | CH 3 | CH 3 | H |
| 100 | CH 3 | H | CH 3 | H | H |
| 101 | H | CF 3 | H | CF 3 | H |
| 102 | CF 3 | CF 3 | H | H | H |
| 103 | H | CF 3 | H | H | CF 3 |
| 104 | CF 3 | H | CF 3 | H | H |
| 105 | H | OCF 3 | H | OCF 3 | H |
| 106 | OCF 3 | OCF 3 | H | H | H |
| 107 | H | OCF 3 | H | H | OCF 3 |
| 108 | OCF 3 | H | OCF 3 | H | H |
| 109 | H | CH 3 | Cl | H | H |
| 110 | H | CH 3 | H | Cl | H |
| 111 | H | H | Cl | CH 3 | H |
| 112 | H | Cl | H | CH 3 | H |
| 113 | Cl | CH 3 | H | H | H |
| 114 | H | CH 3 | H | H | Cl |
| 115 | H | Br | CH 3 | H | H |
| 116 | H | H | CH 3 | Cl | H |
| 117 | H | CH 3 | NO 2 | H | H |
| 118 | H | CH 3 | H | NO 2 | H |
| 119 | H | CH 3 | H | OCH 3 | H |
| 120 | NO 2 | CH 3 | H | H | H |
| 121 | H | Cl | H | CF 3 | H |
| 122 | CF 3 | Cl | H | H | H |
| 123 | H | Cl | H | NO 2 | H |
| 124 | NO 2 | Cl | H | H | H |
| 125 | H | CF 3 | H | Br | H |
| 126 | H | CF 3 | H | NO 2 | H |
| 127 | H | H | CF 3 | NO 2 | H |
| 128 | H | H | CF 3 | Cl | H |
| 129 | H | CF 3 | H | CN | H |
| 130 | H | Cl | H | CN | H |
| 131 | H | NO 2 | H | CN | H |
| 132 | H | NO 2 | H | CH 3 | H |
| 133 | H | NO 2 | H | CF 3 | H |
| 134 | H | NO 2 | H | Cl | H |
| 135 | Cl | NO 2 | H | H | H |
| 136 | H | H | NO 2 | CH 3 | H |
| 137 | H | H | NO 2 | Cl | H |
| 138 | H | CN | F | H | H |
| 139 | H | CN | H | NO 2 | H |
| 140 | H | CN | H | Cl | H |
| 141 | CH 3 | CN | H | H | H |
| 142 | H | Cl | Cl | Cl | H |
| 143 | Cl | Cl | Cl | H | H |
| 144 | Cl | Cl | H | Cl | H |
| 145 | H | Cl | H | Cl | Cl |
| 146 | Cl | H | Cl | Cl | H |
| 147 | H | CH 3 | H | CH 3 | CH 3 |
| 148 | H | OCH 3 | H | OCH 3 | OCH 3 |
| 149 | H | Cl | Cl | Br | H |
| 150 | H | F | H | F | Cl |
| 151 | H | CH 3 | H | Br | Br |
| 152 | H | CF 3 | H | Cl | Cl |
| 153 | H | CF 3 | H | Br | Br |
| 154 | H | F | H | Cl | Br |
| 155 | H | Cl | H | NO 2 | Cl |
| 156 | H | Br | H | NO 2 | Br |
| 157 | H | Cl | H | CN | Cl |
| 158 | H | Cl | H | CF 3 | Cl |
| 159 | H | Br | H | CF 3 | Br |
| 160 | H | Cl | CH 3 | H | Cl |
| 161 | H | Cl | H | CONH 2 | Cl |
| 162 | H | Cl | H | CO 2CH 3 | Cl |
| 163 | H | Cl | H | NHCOCH 3 | Cl |
| 164 | H | Cl | H | OCF 3 | Cl |
| 165 | H | Br | H | F | Br |
| 166 | H | Br | H | CH 3 | Br |
| 167 | H | Cl | H | COCH 3 | Cl |
| 168 | Cl | Cl | H | NO 2 | H |
| 169 | H | F | H | F | Cl |
| 170 | H | Cl | H | CF 3 | Br |
| 171 | H | CH 3 | H | NO 2 | Cl |
| 172 | H | CH 3 | H | NO 2 | Br |
| 173 | H | CH 3 | H | Cl | NO 2 |
| 174 | H | CH 3 | H | Br | NO 2 |
| 175 | H | NO 2 | H | CF 3 | Cl |
| 176 | H | NO 2 | H | CF 3 | Br |
| 177 | H | F | H | Br | Br |
| 178 | H | CN | H | Cl | Cl |
| 179 | H | CN | H | Br | Br |
| 180 | F | F | F | H | F |
Table 6: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 181-360, is corresponding in turn to the 1-180 of table 5.
Table 7: work as A=NH, R
1=CF
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 361-540, is corresponding in turn to the 1-180 of table 5.
Table 8: work as A=NH, R
1=CHF
2, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 541-720, is corresponding in turn to the 1-180 of table 5.
Table 9: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 721-900, is corresponding in turn to the 1-180 of table 5.
Table 10: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=C1, substituting group
r9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 901-1080, is corresponding in turn to the 1-180 of table 5.
Table 11: work as A=NH, R
1=CF
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 1081-1260, is corresponding in turn to the 1-180 of table 5.
Table 12: work as A=NH, R
1=CHF
2, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 1261-1440, is corresponding in turn to the 1-180 of table 5.
Table 13: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 1441-1620, is corresponding in turn to the 1-180 of table 5.
Table 14: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 1621-1800, is corresponding in turn to the 1-180 of table 5.
Table 15: work as A=NH, R
1=CF
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 1801-1980, is corresponding in turn to the 1-180 of table 5.
Table 16: work as A=NH, R
1=CHF
2, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 1981-2160, is corresponding in turn to the 1-180 of table 5.
Table 17: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 2161-2340, is corresponding in turn to the 1-180 of table 5.
Table 18: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 2341-2520, is corresponding in turn to the 1-180 of table 5.
Table 19: work as A=NH, R
1=Cl, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 2521-2700, is corresponding in turn to the 1-180 of table 5.
Table 20: work as A=NH, R
1=CHF
2, R
2=Cl, R
3=CH
3, R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 2701-2880, is corresponding in turn to the 1-180 of table 5.
Table 21: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
5=R
7=H, R
4=CH
3time, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 2881-3060, is corresponding in turn to the 1-180 of table 5.
Table 22: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
5=R
7=H, R
4=CH
3time, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 3061-3240, is corresponding in turn to the 1-180 of table 5.
Table 23: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
5=H, R
4=CH
3, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 3241-3420, is corresponding in turn to the 1-180 of table 5.
Table 24: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
5=H, R
4=CH
3, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 3421-3600, is corresponding in turn to the 1-180 of table 5.
Table 25: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
7=H, R
4=R
5=CH
3time, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 3601-3780, is corresponding in turn to the 1-180 of table 5.
Table 26: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
7=H, R
4=R
5=CH
3time, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 3781-3960, is corresponding in turn to the 1-180 of table 5.
Table 27: work as A=NH, R
1=CH
3, R
2=Cl, R
3=H, R
4=R
5=CH
3, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 3961-4140, is corresponding in turn to the 1-180 of table 5.
Table 28: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=H, R
4=R
5=CH
3, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 4141-4320, is corresponding in turn to the 1-180 of table 5.
Table 29: work as A=O, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 4321-4500, is corresponding in turn to the 1-180 of table 5.
Table 30: work as A=O, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 4501-4680, is corresponding in turn to the 1-180 of table 5.
Table 31: work as A=O, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 4681-4860, is corresponding in turn to the 1-180 of table 5.
Table 32: work as A=O, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=C1, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 4861-5040, is corresponding in turn to the 1-180 of table 5.
Table 33: work as A=S, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 5041-5220, is corresponding in turn to the 1-180 of table 5.
Table 34: work as A=S, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 5221-5400, is corresponding in turn to the 1-180 of table 5.
Table 35: work as A=S, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 5401-5580, is corresponding in turn to the 1-180 of table 5.
Table 36: work as A=S, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
12, R
13consistent with table 5, representation compound is numbered 5581-5760, is corresponding in turn to the 1-180 of table 5.
In general formula I-B,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
11, R
12, R
13for different substituting groups, in table 37, representation compound is numbered 5761-5802.
Table 37
| Numbering | R 9 | R 11 | R 12 | R 13 |
| 5761 | H | H | H | H |
| 5762 | H | H | H | F |
| 5763 | H | H | H | Cl |
| 5764 | H | H | H | Br |
| 5765 | Cl | H | H | H |
| 5766 | H | H | Cl | H |
| 5767 | H | H | Br | H |
| 5768 | H | Cl | H | H |
| 5769 | H | H | H | NO 2 |
| 5770 | NO 2 | H | H | H |
| 5771 | H | H | NO 2 | H |
| 5772 | H | H | CN | H |
| 5773 | H | H | OCF 3 | H |
| 5774 | H | H | H | CH 3 |
| 5775 | CH 3 | H | H | H |
| 5776 | H | H | CH 3 | H |
| 5777 | H | CH 3 | H | H |
| 5778 | H | H | H | CF 3 |
| 5779 | CF 3 | H | H | H |
| 5780 | H | H | CF 3 | H |
| 5781 | H | H | H | OCH 3 |
| 5782 | OCH 3 | H | H | H |
| 5783 | H | H | OCH 3 | H |
| 5784 | H | OCH 3 | H | H |
| 5785 | H | H | Cl | Cl |
| 5786 | Cl | Cl | H | H |
| 5787 | H | H | NO 2 | Cl |
| 5788 | H | H | CN | Cl |
| 5789 | H | H | CF 3 | Cl |
| 5790 | H | H | NO 2 | Br |
| 5791 | Cl | H | H | NO 2 |
| 5792 | H | H | Cl | NO 2 |
| 5793 | H | H | CN | CH 3 |
| 5794 | CH 3 | H | Br | H |
| 5795 | CH 3 | H | NO 2 | H |
| 5796 | CH 3 | CH 3 | H | H |
| 5797 | H | H | Cl | CF 3 |
| 5798 | H | Cl | H | CF 3 |
| 5799 | CH 3 | CH 3 | Cl | Cl |
| 5800 | H | Cl | Cl | Cl |
| 5801 | H | Cl | CF 3 | Br |
| 5802 | CH 3 | H | Br | Br |
Table 38: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 5803-5844, is corresponding in turn to the 5761-5802 of table 37.
Table 39: work as A=NH, R
1=CF
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 5845-5886, is corresponding in turn to the 5761-5802 of table 37.
Table 40: work as A=NH, R
1=CHF
2, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 5887-5928, is corresponding in turn to the 5761-5802 of table 37.
Table 41: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 5929-5970, is corresponding in turn to the 5761-5802 of table 37.
Table 42: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 5971-6012, is corresponding in turn to the 5761-5802 of table 37.
Table 43: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 6013-6054, is corresponding in turn to the 5761-5802 of table 37.
Table 44: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 6055-6096, is corresponding in turn to the 5761-5802 of table 37.
Table 45: work as A=O, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 6097-6138, is corresponding in turn to the 5761-5802 of table 37.
Table 46: work as A=O, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 6139-6180, is corresponding in turn to the 5761-5802 of table 37.
Table 47: work as A=S, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 6181-6222, is corresponding in turn to the 5761-5802 of table 37.
Table 48: work as A=S, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
12, R
13consistent with table 37, representation compound is numbered 6223-6264, is corresponding in turn to the 5761-5802 of table 37.
In general formula I-C,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
10, R
12, R
13for different substituting groups, in table 49, representation compound is numbered 6265-6282.
Table 49
| Numbering | R 9 | R 10 | R 12 | R 13 |
| 6265 | H | H | H | H |
| 6266 | H | Cl | H | H |
| 6267 | H | OCH 3 | H | H |
| 6268 | H | OCH 2CF 3 | H | H |
| 6269 | H | H | H | CH 3 |
| 6270 | H | H | H | CF 3 |
| 6271 | H | H | Br | H |
| 6272 | H | H | CF 3 | H |
| 6273 | H | H | OCH 3 | H |
| 6274 | Cl | Cl | H | H |
| 6275 | H | Cl | Cl | H |
| 6276 | Cl | H | Cl | H |
| 6277 | H | Cl | H | CH 3 |
| 6278 | CH 3 | Cl | H | H |
| 6279 | H | Cl | CH 3 | H |
| 6280 | H | Cl | Cl | CF 3 |
| 6281 | Cl | H | NHCH 3 | H |
| 6282 | Cl | H | SO 2CH 3 | H |
Table 50: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
12, R
13consistent with table 49, representation compound is numbered 6283-6300, is corresponding in turn to the 6265-6282 of table 49.
Table 51: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
12, R
13consistent with table 49, representation compound is numbered 6301-6318, is corresponding in turn to the 6265-6282 of table 49.
Table 52: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
12, R
13consistent with table 49, representation compound is numbered 6319-6336, is corresponding in turn to the 6265-6282 of table 49.
Table 53: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
12, R
13consistent with table 49, representation compound is numbered 6337-6354, is corresponding in turn to the 6265-6282 of table 49.
Table 54: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
12, R
13consistent with table 49, representation compound is numbered 6355-6372, is corresponding in turn to the 6265-6282 of table 49.
In general formula I-D,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
10, R
11, R
13for different substituting groups, in table 55, representation compound is numbered 6373-6380.
Table 55
| Numbering | R 9 | R 10 | R 11 | R 13 |
| 6373 | Cl | H | H | H |
| 6374 | H | H | H | Br |
| 6375 | H | Cl | H | Cl |
| 6376 | OCH 3 | H | H | H |
| 6377 | OCH 3 | H | OCH 3 | H |
| 6378 | OCH 3 | H | Cl | H |
| 6379 | NHCH 3 | H | Cl | H |
| 6380 | Cl | Cl | Cl | Cl |
Table 56: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
13consistent with table 55, representation compound is numbered 6381-6388, is corresponding in turn to the 6373-6380 of table 55.
Table 57: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
13consistent with table 55, representation compound is numbered 6389-6396, is corresponding in turn to the 6373-6380 of table 55.
Table 58: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
13consistent with table 55, representation compound is numbered 6397-6404, is corresponding in turn to the 6373-6380 of table 55.
Table 59: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
13consistent with table 55, representation compound is numbered 6405-6412, is corresponding in turn to the 6373-6380 of table 55.
Table 60: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
13consistent with table 55, representation compound is numbered 6413-6420, is corresponding in turn to the 6373-6380 of table 55.
In general formula I-E,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
10, R
11, R
13for different substituting groups, in table 61, representation compound is numbered 6421-6424.
Table 61
| Numbering | R 9 | R 11 | R 12 |
| 6421 | H | H | H |
| 6422 | CH 3 | CH 3 | H |
| 6423 | OCH 3 | OCH 3 | H |
| 6424 | CF 3 | CO 2C 2H 5 | H |
Table 62: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
13consistent with table 61, representation compound is numbered 6425-6428, is corresponding in turn to the 6421-6424 of table 61.
Table 63: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
13consistent with table 61, representation compound is numbered 6429-6432, is corresponding in turn to the 6421-6424 of table 61.
Table 64: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
11, R
13consistent with table 61, representation compound is numbered 6433-6436, is corresponding in turn to the 6421-6424 of table 61.
Table 65: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
13consistent with table 61, representation compound is numbered 6437-6440, is corresponding in turn to the 6421-6424 of table 61.
Table 66: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
11, R
13consistent with table 61, representation compound is numbered 6441-6444, is corresponding in turn to the 6421-6424 of table 61.
In general formula I-F,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
11, R
13for different substituting groups, in table 67, representation compound is numbered 6445-6448.
Table 67
| Numbering | R 9 | R 11 | R 13 |
| 6445 | H | H | H |
| 6446 | Cl | H | H |
| 6447 | Cl | CH 3 | H |
| 6448 | Cl | H | Cl |
Table 68: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
11, R
13consistent with table 67, representation compound is numbered 6449-6452, is corresponding in turn to the 6445-6448 of table 67.
Table 69: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
11, R
13consistent with table 67, representation compound is numbered 6453-6456, is corresponding in turn to the 6445-6448 of table 67.
Table 70: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
11, R
13consistent with table 67, representation compound is numbered 6457-6460, is corresponding in turn to the 6445-6448 of table 67.
Table 71: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
11, R
13consistent with table 67, representation compound is numbered 6461-6464, is corresponding in turn to the 6445-6448 of table 67.
Table 72: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
11, R
13consistent with table 67, representation compound is numbered 6465-6468, is corresponding in turn to the 6445-6448 of table 67.
In general formula I-G,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
10, R
13for different substituting groups, in table 73, representation compound is numbered 6469-6470.
Table 73
| Numbering | R 9 | R 10 | R 12 |
| 6469 | H | H | H |
| 6470 | Cl | H | H |
Table 74: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
13consistent with table 73, representation compound is numbered 6471-6472, is corresponding in turn to the 6469-6470 of table 73.
Table 75: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
13consistent with table 73, representation compound is numbered 6473-6474, is corresponding in turn to the 6469-6470 of table 73.
Table 76: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
13consistent with table 73, representation compound is numbered 6475-6476, is corresponding in turn to the 6469-6470 of table 73.
Table 77: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
13consistent with table 73, representation compound is numbered 6477-6478, is corresponding in turn to the 6469-6470 of table 73.
Table 78: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
13consistent with table 73, representation compound is numbered 6479-6480, is corresponding in turn to the 6469-6470 of table 73.
In general formula I-H,
Work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7during=H, R
9, R
10, R
13for different substituting groups, in table 79, representation compound is numbered 6481-6482.
Table 79
| Numbering | R 9 | R 10 | R 13 |
| 6481 | H | H | H |
| 6482 | H | Cl | H |
Table 80: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7during=H, substituent R
9, R
10, R
13consistent with table 79, representation compound is numbered 6483-6484, is corresponding in turn to the 6481-6482 of table 79.
Table 81: work as A=NH, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
13consistent with table 79, representation compound is numbered 6485-6486, is corresponding in turn to the 6481-6482 of table 79.
Table 82: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=H, R
7during=Cl, substituent R
9, R
10, R
13consistent with table 79, representation compound is numbered 6487-6488, is corresponding in turn to the 6481-6482 of table 79.
Table 83: work as A=NH, R
1=CH
3, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
13consistent with table 79, representation compound is numbered 6489-6490, is corresponding in turn to the 6481-6482 of table 79.
Table 84: work as A=NH, R
1=C
2h
5, R
2=Cl, R
3=CH
3, R
4=R
5=R
7during=H, substituent R
9, R
10, R
13consistent with table 79, representation compound is numbered 6491-6492, is corresponding in turn to the 6481-6482 of table 79.
In general formula I-A, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
10=R
11=R
13during=H, R
12=Cl, substituent R
14in table 85, representation compound is numbered 6493-6632.
Table 85
Table 86: in general formula I-A, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
11=R
13during=H, R
10=R
12=Cl, substituent R
14consistent with table 85, representation compound is numbered 6633-6772, is corresponding in turn to the 6493-6632 of table 85.
Table 87: in general formula I-A, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
10=R
11=R
13during=H, R
12=CF
3, substituent R
14consistent with table 85, representation compound is numbered 6773-6912, is corresponding in turn to the 6493-6632 of table 85.
Table 88: in general formula I-B, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
11=R
13during=H, R
12=Cl, substituent R
14consistent with table 85, representation compound is numbered 6913-7052, is corresponding in turn to the 6493-6632 of table 85.
Table 89: in general formula I-B, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
11=R
13during=H, R
12=CF
3, substituent R
14consistent with table 85, representation compound is numbered 7053-7192, is corresponding in turn to the 6493-6632 of table 85.
Table 90: in general formula I-B, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
11during=H, R
12=CF
3, R
13=Cl substituent R
14consistent with table 85, representation compound is numbered 7193-7332, is corresponding in turn to the 6493-6632 of table 85.
Table 91: in general formula I-B, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
11during=H, R
12=R
13=Cl, substituent R
14consistent with table 85, representation compound is numbered 7333-7472, is corresponding in turn to the 6493-6632 of table 85.
Table 92: in general formula I-C, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
12=R
13during=H, R
10=Cl, substituent R
14consistent with table 85, representation compound is numbered 7473-7612, is corresponding in turn to the 6493-6632 of table 85.
Table 93: in general formula I-D, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
10=R
13during=H, R
9=R
11=Cl, substituent R
14consistent with table 85, representation compound is numbered 7613-7752, is corresponding in turn to the 6493-6632 of table 85.
Table 94: in general formula I-E, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
12during=H, R
9=R
11=OCH
3, substituent R
14consistent with table 85, representation compound is numbered 7753-7892, is corresponding in turn to the 6493-6632 of table 85.
Table 95: in general formula I-E, work as A=NR
14, R
1=C
2h
5, R
2=Cl, R
3=R
4=R
5=R
7=R
12during=H, R
9=R
11=CH
3, substituent R
14consistent with table 85, representation compound is numbered 7893-8032, is corresponding in turn to the 6493-6632 of table 85.
Table 96: in general formula I-F, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
11during=H, R
9=CH
3, R
13=Cl, substituent R
14consistent with table 85, representation compound is numbered 8033-8172, is corresponding in turn to the 6493-6632 of table 85.
Table 97: in general formula I-G, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
10=R
12during=H, R
9=Cl, substituent R
14consistent with table 85, representation compound is numbered 8173-8312, is corresponding in turn to the 6493-6632 of table 85.
Table 98: in general formula I-H, work as A=NR
14, R
1=CH
3, R
2=Cl, R
3=R
4=R
5=R
7=R
9=R
13during=H, R
10=Cl, substituent R
14consistent with table 85, representation compound is numbered 8313-8452, is corresponding in turn to the 6493-6632 of table 85.
The salt of part of compounds of the present invention can illustrate with the salt of the particular compound listed in table 99, but does not limit the present invention.
Table 99 part of compounds salt
The compounds of this invention is prepared in accordance with the following methods, and reaction formula is as follows, and in formula, each group unless otherwise indicated defines ditto:
Intermediate II and III are obtained by reacting compound of Formula I in the basic conditions.
The suitable optional potassium hydroxide freely of alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine, sodium methylate, sodium ethylate, sodium hydride, potassium tert.-butoxide or sodium tert-butoxide etc.
React and carry out in suitable solvent, the suitable optional tetrahydrofuran (THF) freely of solvent, Isosorbide-5-Nitrae-dioxane, acetonitrile, toluene, dimethylbenzene, benzene, DMF, N-Methyl pyrrolidone, methyl-sulphoxide, acetone or butanone etc.
Temperature of reaction between room temperature to solvent boiling point temperature, can be generally 20-100 DEG C.
Reaction times is 30 minutes to 20 hours, usual 1-10 hour.
Intermediate II part has commercially available, also can prepare by known method, such as reference literature JP2000007662, US4977264, US6090815, US20040092402, JP09124613, US5468751, US4985426, US4845097, RecueildesTravauxChimiquesdesPays-Bas (1978), 97 (11), Pages288-92, JournaloftheAmericanChemicalSociety, 79,1455(1957), JournalofChemicalSociety, the method p.3478-3481(1955) described prepare.
Intermediate III is different according to A, B definition, is divided into following three kinds of situations preparation:
The first situation:
As A=NH,
1) B=-CH
2in-time, referring to the method preparation described in patent WO9404527, US20110054173 or WO2011025505.Or be prepared as follows:
In formula, U is leavings group, is halogen or hydroxyl etc.
Intermediate compound I X-1 and X-1, under suitable alkali exists, at suitable temperature, reacts 30 minutes to 20 hours, usual 1-10 hour, obtained intermediate VIII-1 in suitable solvent; VIII-1 obtains VII-1 through red aluminium reducing, and this step working method is referring to patent EP1840128; VII-1 and sulfur oxychloride react obtained VI-1, and this is normal experiment method; VI-1 and sodium hydride react, obtained V-1, this step working method referring to patent WO2007045989, WO2009115257, according to JournalofOrganicChemistry, 71 (21), 8023-8027; 2006, Synthesis, (24), 4242-4250,2010, Heterocycles, 56 (1-2), 443-455,2002 or ARKIVOC (Gainesville, FL, UnitedStates) [onlinecomputerfile], (10), 40-51, the method described in 2002, obtains IV-1 by V-1; Finally, IV-1 obtains intermediate III-1 through hydrogenating reduction at suitable catalyzer under existing with ammoniacal liquor, and 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); OrganicSyntheses, Coll.Vol.3, p.229, p.720 (1955), Vol.23, p.71 (1943) or Vol.27, the method p.18 described in (1947) is carried out.Suitable catalyzer can be selected from Raney's nickel, palladium carbon or platinum oxide etc.
Intermediate source is as follows: intermediate compound I X-1 and X-1 all has commercially available, or conventionally prepares.
The suitable optional potassium hydroxide freely of alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine, sodium methylate, sodium ethylate, sodium hydride, potassium tert.-butoxide or sodium tert-butoxide etc.
React and carry out in suitable solvent, the suitable optional tetrahydrofuran (THF) freely of solvent, Isosorbide-5-Nitrae-dioxane, acetonitrile, toluene, dimethylbenzene, benzene, DMF, N-Methyl pyrrolidone, methyl-sulphoxide, acetone or butanone etc.
Temperature of reaction between room temperature to solvent boiling point temperature, can be generally 20-100 DEG C.
Reaction times is 30 minutes to 20 hours, usual 1-10 hour.
2) B=-CH
2cH
2in-time, preparation method is as follows:
IV-2 is prepared with reference to Synthesis, (9), 727-9 by IV-1; 1983 or TetrahedronLetters, 39 (51), 9455-9456; The method described in 1998 is carried out; The same B=-CH of III-2 method is prepared by IV-2
2-time corresponding steps.
The second situation: work as A=NR
14(but R
14≠ H) time, by R
14the intermediate of=H is that raw material obtains, and concrete operations are carried out see the method described in WO2004093800A.
The third situation: as A=O or S, the method described in preparation method referenced patent WO2012075917.
The preparation method of compound of Formula I salt is as follows:
In compound of Formula I, the preparation of PYRIMITHAMINE salify, as follows:
By A=NR
14general formula I-1 compound obtain corresponding salt I-2 with organic acid or inorganic acid reaction, reaction formula is as follows:
In addition, the nitrogen in pyrimidine ring and other nitrogen heterocyclic rings also can salify, and preparation method can reference DE19647317, JP2001504473, US5925644, WO9822446, ZA9710187 etc.
General formula I-1 reacts with organic acid or inorganic acids and usually carries out in room temperature to solvent boiling point temperature range, and comparatively suitable temperature of reaction is 20 ~ 100 DEG C.Reaction times is 30 minutes to 20 hours, usual 1 ~ 10 hour.Suitable solvent can be selected from water, methyl alcohol, ethanol, Virahol, benzene,toluene,xylene, acetone, methylethylketone, mibk, chloroform, methylene dichloride, methyl acetate, ethyl acetate, tetrahydrofuran (THF), diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.
Can comprise with the acid of general formula I-1 compound salify of the present invention: hydrochloric acid, sulfuric 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 etc.; Preferred hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid or tosic acid further.
Although some compound also belongs to and replaces fragrant oxy picolinate compounds disclosed in compound of Formula I of the present invention and prior art, still there is remarkable difference in constitutional features.And make compound of the present invention have better sterilization and/or pesticide and miticide actility due to these structural differences.
Compound of Formula I demonstrates excellent activity to the multiple germ in agricultural or other field, also demonstrates good activity to insect evil mite.Therefore, technical scheme of the present invention also comprises the purposes that compound of Formula I is used as to prepare sterilant, insecticidal/acaricidal agent in agricultural or other field.
The example of the disease mentioned below is only used for the present invention is described, but never limits the present invention.
Compound of Formula I can be used for preventing and treating following disease: oomycetes diseases, as oidium (cucumber downy mildew, oilseed rape downy mildew, downy mildew, beet oidium, downy mildew of sugarcane, tobacco downy mildew, pea oidium, sponge gourd oidium, wax gourd oidium, muskmelon downy mildew, cabbage oidium, downy mildew of spinach, radish oidium, downy mildew of garpe, onion mildew), white rust (white rust of colza, cabbage white blister), samping off (rape samping off, Tobacco seedling diseases, tomato samping off, capsicum samping off, eggplant samping off, cucumber samping off, cotton seedling samping off), phytophthora rot (capsicum phytophthora rot, sponge gourd phytophthora rot, wax gourd phytophthora rot), epidemic disease (broad bean epidemic disease, Cucumber Blight, pumpkin epidemic disease, wax gourd epidemic disease, watermelon epidemic disease, muskmelon blight, capsicum epidemic disease, leek epidemic disease, garlic epidemic disease, Cotton blight), late blight (the late blight of potato, tomato late blight) etc., imperfect fungi disease, as blight (sweet potato blight, cotton wilt, sesame blight, castor-oil plant blight, tomato wilt, Kidney bean blight, cucumber fusarium axysporum, sponge gourd blight, pumpkin blight, wax gourd blight, watermelon blight, Muskmelon Fusarium wilt, capsicum wilt, faba bean Fusarium wilt, rape blight, soybean Fusariuming disease), root rot (Fusarium solani, Fructus Solani melongenae root maize ear rot, Bean Root maize ear rot, cucumber root rot, Root of Balsampear maize ear rot, cotton black root rot, root rot of Vicia faba), damping-off (cotton seedling blight, sesame damping-off, capsicum damping-off, cucumber rhizoctonia rot, Chinese cabbage damping-off), anthrax (anthracnose of sorghum, cotton anthracnose, bluish dogbane anthrax, jute anthrax, anthracnose of flax, Colletotricum destructivum, mulberry anthrax, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, balsam pear anthrax, summer squash anthrax, wax gourd anthrax, watermelon anthrax, muskmelon anthrax, lichee anthrax), verticillium (cotton verticillium wilt, Sunflower Receptacle verticillium, tomato verticillium, capsicum verticillium, eggplant verticillium wilt), black spot (summer squash black spot, wax gourd black spot, muskmelon black spot), gray mold (cotton boll gray mold, bluish dogbane gray mold, graw mold of tomato, Botrytis cinerea, Kidney bean gray mold, celery gray mold, spinach gray mold, Kiwifruit gray mold), brown spot (cotton brown spot, jute brown spot, beet cercospora leaf spot, the cercospora brown spot of peanut, capsicum brown spot, wax gourd brown spot, Soybean Brown Spot pinta, septorial brown spot of sunflower, pea brown spot, broad bean brown spot), black spot (the false black spot of flax, alternaria stem rot of colza, sesame black spot, Sunflower Receptacle black spot, castor-oil plant black spot, tomato black spot, capsicum black spot, eggplant black spot, Kidney bean black spot, cucumber black spot, celery black spot, carrot black rot, black rot of carrot, melanose or canker of apple, the cercospora black spot of peanut), spot blight (spotted wilt of tomato, cayenne pepper spots rot, celery septoria disease), early blight (early blight of tomato, capsicum early blight, eggplant early blight, target, early blight of celery), ring spot (soybean ring spot, sesame ring spot, Kidney bean ring spot), leaf blight (sesame leaf rot, Sunflower Leaf rot, watermelon leaf rot, Muskmelon leaf rot), base rot disease (tomato base rot disease, Kidney bean base rot disease), and other (Helminthosporium carbonum, bluish dogbane waist folding is sick, rice blast, the black sheath of chestnut is sick, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem rot, soybean diplostomiasis, muskmelon leaf blight, Peanut Web Blotch Disease, the red leaf spot of tea, pepper white star disease, Leaf of Chinese Waxgourd pinta, celery Black Rotten, spinach heartrot, bluish dogbane leaf mold, bluish dogbane spot disease, jute stem pinta, purple spot of soybean, Alternaria sesami, castor-oil plant graywall, dark brown leaf spot, cercospora leaf spot of egg plant, Kidney bean red spot disease, balsam pear leukodermia, watermelon spot disease, jute withered rotten disease, Sunflower Root stem rot, Kidney bean charcoal rot, soybean target spot is sick, eggplant rod spore leaf spot, Leaf Spot Caused by Corynespora cassiicola on Cucumber, leaf muld of tomato, eggplant leaf mold, broad bean reddish macules etc.) etc., basidiomycetes disease, as rust (stripe rust of wheat, the stem rust of wheat, wheat leaf rust, Peanut Rust, rust of sunflower, sugarcane rust, leek rust, rust of onion, chestnut rust, soybean rust), smut (maize head smut, corn smut, head smut of sorghum, sorghum loose smut, covered kernel smut of kaoliang, high beam column smut disease, chestnut kernel smut, smut of sugarcane, Bean rust disease) and other (as wheat hypochnus, rice sheath blight diseases etc.) etc., ascomycetes disease, as Powdery Mildew (wheat powdery mildew, rape Powdery Mildew, sesame Powdery Mildew, Sunflower Receptacle Powdery Mildew, beet powdery mildew, eggplant Powdery Mildew, powdery mildew of pea, sponge gourd Powdery Mildew, squash marble dust, Pumpkin powdery mildew, wax gourd Powdery Mildew, melon powdery mildew, uncinula necator, broad bean Powdery Mildew), sclerotium disease (flax sclerotium disease, sclerotinia rot of colza, soybean sclerotinia crown rot, peanut sclerotium disease, tobacco sclerotium disease, capsicum sclerotium disease, eggplant sclerotium disease, bean sclerotinia rot, pea sclerotium disease, cucumber timberrot, balsam pear sclerotium disease, wax gourd sclerotinia, watermelon sclerotium disease, celery sclerotium disease), black spot (scab of apple, pear scab) etc.Especially, to corn rust, rice blast, gray mold of cucumber and cucumber downy mildew, at lower doses still there is good prevention effect.
Compound of Formula I can be used for preventing and treating following insect: Coleoptera (Coleoptera) (beetle): bean weevil belongs to kind of (Acanthoscelidesspp.) (curculionid), acanthoscelides obtectus (Acanthoscelidesobtectus) (common pea weevil), Emerald ash borer (Agrilusplanipennis) (emerald ash borer, Agrilus planipennis), acupuncture needle Eimeria kind (Agriotesspp.) (wireworm), Anoplophora glabripenis (Anoplophoraglabripennis) (Asia psacotheahilaris), cotton boll resembles and belongs to kind of (Anthonomusspp.) (Culculionidae), Mexico's cotton boll resembles (Anthonomusgrandis) (bollworm), cocoon honeybee belongs to kind of (Aphidiusspp.), weevil belongs to kind of (Apionspp.) (curculionid), sugarcane cockchafer belongs to kind of (Apogoniaspp.) (grub), black suede cockchafer (Atacniussprctulus) (smaller velvety chafer), Atomaria linearis (Atomarialinearis) (little beet beetle (pygmymangoldbeetle), cucumber beetle belongs to kind of (Aulacophorespp.), beet resembles (Bothynoderespunctiventris) (beet tails curculionid), bean weevil belongs to kind of (Bruchusspp.) (curculionid), pea weevil (Bruchuspisorum) (pea weevil), Cacoesia belongs to kind of (Cacoesiaspp.), Callosobruchus maculatus (Callosobruchusmaculatus) (southern cowpea curculionid), pineapple bug (Carpophilushemipteras) (dried-frait beetle), beet tortoise beetle (Cassidavittata), it Bos kind (Ccrostcrnaspp.), Ccrotoma belongs to kind of (Ccrotomaspp.) (chrysomonad (chrysomcids)), beans chrysomelid (Cerotomatrifurcata) (the chrysomelid worm of beans), tortoise resembles and belongs to kind of (Ceutorhynchusspp.) (curculionid), Chinese cabbage seed tortoise resembles (Ceutorhynchusassimilis) (Chinese cabbage weevil (cabbageseedpodweevil)), turnip tortoise resembles (Ceutorhynchusnapi) (Caulis et Folium Brassicae capitatae curculionid (cabbagecurculio)), phyllotreta kind (Chaetocnemaspp.) (chrysomonad), Colaspis belongs to kind of (Colaspisspp.) (a native beetle), Conoderusscalaris, Conoderusstigmosus, Lee resembles (Conotrachelusnenuphar) (plum cone weevil), Cotinusnitidis (Green june beetle (GreenJunebeetle)), officinalis scotellaris (Criocerisasparagi) (officinalis beetle), rusty grain beetle (Cryptolestesferrugincus) (rust paddy beetle (rustygrainbeetle)), Cryptolestes pusillus (Cryptolestespusillus) (flat ostomatid), Cryptolestes turcicus Grouville (Cryptolestesturcicus) (Turkey paddy beetle (Turkishgrainbeetle)), Ctenicera belongs to kind of (Cteniceraspp.) (nematode), Curculio kind (Curculiospp.) (curculionid), round end rhinoceros cockchafer belongs to kind of (Cyclocephalaspp.) (grub), close some withe resembles (Cylindrocpturusadspersus) (Sunflower Receptacle grass curculionid (sunflowerstemweevil)), mango leaf-cutting resembles (Deporausmarginatus) (mango leaf-cutting curculionid (mangoleaf-cuttingweevil)), lader beetle stupid (Dermesteslardarius) (lader beetle is stupid), white abdomen skin stupid (Dermestesmaculates) (white abdomen skin is stupid), chrysomelid genus kind of (Diabroticaspp.) (chrysomelid), mexican bean ladybird (Epilachnavarivcstis) (Mexico beans beetle), moth stem weevil (raustinuscubae), pale collar resembles (Hylobiuspales) (pales weevil (palesweevil)), Phytonomus kind (Hyperaspp.) (curculionid), alfalfa leaf resembles (Hyperapostica) (alfalfa weevil), Hyperdoes belongs to kind of (Hyperdoesspp.) (an Argentinian stem weevil (Hyperodesweevil)), coffee cherry little stupid (Hypothenemushampei) (coffee cherry beetle), little stupid genus kind of (Ipsspp.) (sour jujube shin little stupid (engravers)) of tooth, lasioderma serricorne (Lasiodermaserricorne) (cigarette beetle), colorado potato bug (Leptinotarsadecemlineata) (Colorado potato beetle), Liogenysfuscus, Liogenyssuturalis, rice water weevil (Lissorhoptrusoryzophilus) (rice water weevil), the stupid genus of powder kind of (Lyctusspp.) (the stupid beetle of wooden stupid moth/powder (powderpostbeetles)), Maecolaspisjoliveti, Megascelis belong to kind of (Megascelisspp.), corn click beetle (Melanotuscommunis), nitidulid belongs to kind of (Meligethesspp.), rape nitidulid (Meligethesaeneus) (brevitarsis (blossombeetle)), May beetle (Melolonthamelolontha) (typical European chafer), Obereabrevis, linear cylinder longicorn (Oberealinearis), coconut palm moth rhinoceros cockchafer (Oryctesrhinoceros) (date palm beetle (datepalmbeetle)), trade saw-toothed grain beetle (Oryzaephilusmercator) (market saw-toothed grain beetle (merchantgrainbeetle)), saw-toothed grain beetle (Oryzaephilussurinamensis) (sawtooth paddy beetle (sawtoothcdgrainbcctlc)), beak weevil belongs to kind of (Otiorhynchusspp.) (curculionid), black angle scotellaris (Oulemamelanopus) (cereal leaf beetle (cerealleafbeetle)), Oulema oryzae (Oulemaoryzae), the short beak of rose resembles and belongs to kind of (Pantomorusspp.) (curculionid), food phyllobranchia cockchafer belongs to kind of (Phyllophagaspp.) (May/June chafer), Phvllophagacuyabana, striped flea beetle kind (Phyllotretaspp.) (chrysomonad), apple tiger resembles and belongs to kind of (Phynchitesspp.), Japan popillia flavosellata fairmaire (Popilliajaponica) (Japanese beetle), large space between muscles stupid (Prostephanustruncates) (large space between muscles long stupid (largergrainborer)), paddy stupid (Rhizoperthadominica) (the little moth of paddy (lessergrainborer)), root gill cockchafer belongs to kind of (Rhizotrogusspp.) (European chafer (Eurpoeanchafer)), Rhynchophorus kind (Rhynchophorusspp.) (curculionid), little stupid genus kind of (Scolytusspp.) (wooden stupid moth), Shenophorus belongs to kind of (Shenophorusspp.) (grain weevil), pea leaf resembles (Sitonalincatus) (pealeaf weevil (pcaleafweevil)), Sitophilus kind (Sitophilusspp.) (grain weevil first), grain weevil (Sitophilusgranaries) (paddy worm (granaryweevil)), rice weevil (Sitophilusoryzae) (rice weevil first (riceweevil)), medicinal material ostomatid (Stegobiumpaniceum) (Stegobium paniceum (drugstorebeetle)), Tribolium kind (Triboliumspp.) (flour beetle), red flour beetle (Triboliumcastaneum) (red flour beetle (redflourbeetle)), assorted plan paddy moistens (Triboliumconfusum) (confused flour beetle (confusedflourbeetle)), piebald skin stupid (Trogodermavariabile) (warehouse skin stupid (warehousebeetle)) and Zabrustenebioides.
Dermaptera (Dcrmaptcra) (earwig).
Neuroptera (Dictyoptera) (cockroach): Groton bug (Blattellagermanica) (Groton bug (Germancockroach)), oriental cockroach (Blattaorientalis) (Blatta seu periplaneta), Pennsylvania wood Lian (Parcoblattapennylvanica), periplaneta americana (Periplanetaamericana) (America roach consumptive disease (Americancockroach)), Australian cockroach (Periplanetaaustraloasiae) (Australian cockroach (Australiancockroach)), periplaneta brunnea (Pcriplanctabrunnca) (periplaneta brunnea (browncockroach)), smoke Perilpaneta americana (Periplanetafuliginosa) (Peroplaneta fluligginosa (smokybrowncockroach)), the green blattaria of sugarcane (Pyncoselussuninamensis) (sugarcane Lian (Surinamcockroach)) and long palpus blattaria (Supellalongipalpa) (brown band blattaria (brownbandedcockroach)).
Diptera (Diptera) (fly): Aedes kind (Aedesspp.) (mosquito), alfalfa is dived fly (Agromyzafrontella) (alfalfa dive fly (alfalfablotchleafminer)), Hippelates kind ((Agromyzaspp.) (Liriomyza), by Anastrepha kind (Anastrephaspp.) (fruit bat), Caribbean is by trypetid (Anastrephasuspensa) (Caribbean is by trypetid (Caribbeanfruitfly)), Anopheles kind (Anophelesspp.) (mosquito), Bactrocera kind (Batroceraspp.) (fruit bat), melon trypetid (Bactroceracucurbitae) (melon fly), citrus fruit fly (Bactroceradorsalis) (oriental fruit fly), little bar Anastrepha kind (Ceratitisspp.) (fruit bat), the little bar trypetid (Ceratitiscapitata) (medfly) in Mediterranean Sea, Chrysops kind (Chrysopsspp.) (deer horsefly), Callitroga's kind (Cochliomyiaspp.) (screw worm fly larva), Ying uranotaenia kind (Contariniaspp.) (Ying mosquito), Culex kind (Culexspp.) (mosquito), Ye Ying uranotaenia kind (Dasineuraspp.) (Ying mosquito), You Cai Ye Ying mosquito (Dasineurabrassicae) (Juan Xin Cai Ying mosquito), Delia kind (Deliaspp.), delia platura (Deliaplatura) (root maggot (seedcornmaggot)), Drosophila kind (Drosophilaspp.) (vinegar fly), Fannia kind (Fanniaspp.) (housefly), anthomyia canicularis (Fanniacanicularis) (Fannia canicularis (littlehousefly)), anthomyia scalaris (Fanniascalaris) (anthomyia scalaris), large horse botfly (Gasterophilusintestinalis) (horse botfly), Gracilliaperseae, Haematobia irritans (Haematobiairritans) (horn fly), Hylemyia kind (Hylemyiaspp.) (root maggot (rootmaggot)), heel fly (Hypodermalineatum) (laiu wire rope torsalo (commoncattlegrub)), Liriomyza kind (Liriomyzaspp.) (Liriomyza), wild cabbage liriomyza bryoniae (Liriomyzabrassica) (Liriomyza that crawls (serpentineleafminer)), sheep hippoboscid (Melophagusovinus) (sheepked), fly belongs to kind of (Muscaspp.) (housefly (muscidfly)), face fly (Muscaautumnalis) (face fly (facefly)), housefly (Vuscadomestica) (housefly (housefly)), Oestrus ovis (Oestrusovis) (sheep nose fly (sheepbotfly)), Europe frit fly (Oscinellafrit) (Oscinella frit), beet spring fly (Pegomyiabetae) (spinach leaf miner (beetleafminer)), wheat fly belongs to kind of (Phorbiaspp.), carrot fly (Psilarosae) (Radix Dauci Sativae rust fly (carrotrustfly)), cherry fruit bat (Rhagoletiscerasi) (cherry fruit bat (cherryfruitfly)), Rhagoletis pomonella (Rhagoletispomonella) (apple maggots (applemaggot)), wheat midge (Sitodiplosismosellana) (orange wheat flower mosquito (orangewheatblossommidge)), tatukira (stomoxyscalcitruns) (tatukira (stablefly)), the gadfly belongs to kind of (Tahanusspp.) (horse botfly) and large uranotaenia kind (Tipulaspp.) (daddy-longlegs).
Hemiptera (Hemiptera) (stinkbug): intend green stinkbug (Acrosternumhilare) (green stinkbug (greenstinkbug)), America paddy chinch bug (Blissusleucopterus) (chinch bug (chinchbug)), potato pretty fleahopper (Calocorisnorvegicus) (potato fleahopper (potatomirid)), cimex hemipterus (Cimexhemipterus) (cimex hemipterus (tropicalbedbug)), bedbug (Cimexlectularius) (bedbug (bedhug)), Daghertusfasciatus, Dichelopsfurcatus, cotton the red stinkbug of black wing (Dysdercussuturellus) (red cotton bug (cottonstainer)), Edessameditabunda, Europe Eurygasterspp (Eurygastermaura) (paddy worm (cerealbug)), Euschistusheros, brown smelly stinkbug (Euschistusservus) (brown stinkbug (brownstinkbug)), iS-One angle fleahopper (Helopeltisantonii), tea angle fleahopper (Helopeltistheivora) (teablightplantbug), stinkbug belongs to kind of (Lagynotomusspp.) (stinkbug), large Leptocorisa spp (Leptocorisaoratorius), different Leptocorisa spp (Leptocorisavaricornis), Lygus Hahn kind (Lygusspp.) (fleahopper (plantbug)), beanpod lygus bug (Lygushesperus) (westerntarnishedplantbug), the graceful powder stinkbug (Maconellicoccushirsutus) of the rose of Sharon, Neurocolpuslongirostris, Nezara viridula smaragdula Fabricius. (Nezaraviridula) (southerngreenstinkbug), Phytocoris kind (PhyLocorisspp.) (fleahopper), fleahopper (Phytocoriscalifornicus) is planted in California, Phytocorisrelativus, Piezodorusguildingi, four line fleahopper (Poecilocapsuslineatus) (fourlinedplantbug), Psallusvaccinicola, Pseudacystaperseae, Scaptocoriscastanea and Triatoma kind (Triatomaspp.) (cone nose worm (bloodsuckingconenosebug) of sucking blood/hunt stinkbug (kissingbug)).
Homoptera (Homoptera) (aphid, a red-spotted lizard, aleyrodid, leafhopper): acyrthosiphum pisim (Acrythosiphonpisum) (acyrthosiphum pisim (peaaphid)), adelgid belongs to kind of (Adelgesspp.) (adelgids), wild cabbage aleyrodid (Aleurodesproletella) (Caulis et Folium Brassicae capitatae aleyrodid), Aleurodicus dispersus (Aleurodicusdisperses), velvet aleyrodid (Aleurothrixusflccosus) (whitefly in bt cotton (woollywhitefly)), white wheel armored scale belongs to kind of (Aluacaspisspp.), Amrascabigutellabigutella, froghopper belongs to kind of (Aphrophoraspp.) (leafhopper (leafhopper)), California red scale (Aonidiellaaurantii) (the red a red-spotted lizard in California (Californiaredscale)), Aphis kind (Aphisspp.) (aphid), cotten aphid (Aphisgossypii) (cottonaphid), apple aphid (Aphispomi) (appleaphid), eggplant is without net aphid (Aulacorthitmsolani) (foxglove aphid (foxgloveaphid)), Aleyrodes kind (Bemisiaspp.) (aleyrodid), Bemisia argentifolii (Bemisiaargentifolii), sweet potato whitefly (Bemisiatabaci) (sweetpotatowhitefly), Diuraphis noxia (Brachycolusnoxius) (Russian aphid (Russianaphid)), officinalis tubule aphid (Brachycoryncliaasparagi) (officinalis aphid (asparagusaphid)), Brevenniarehi, brevicoryne brassicae (Brevicorynebrassicae) (Caulis et Folium Brassicae capitatae aphid), lecanium belongs to kind of (Ceroplastesspp.) (a red-spotted lizard), ceroplastes rubens (Ceroplastesrubens) (redwaxscale), snow armored scale belongs to kind of (Chionaspisspp.) (a red-spotted lizard), Aspidiotus belongs to kind of (Chrysomphalusspp.) (a red-spotted lizard), soft wax a red-spotted lizard belongs to kind of (Coccusspp.) (a red-spotted lizard), the pink bad aphid (Dysaphisplantaginea) (rosyappleaphid) of apple, green jassids belongs to kind of (Empoascaspp.) (leafhopper), apple aphid (Eriosomalanigerum) (woollyappleaphid), blow cotton a red-spotted lizard (Iceryapurchasi) (cottonycushionscale), mango yellow line leafhopper (Idioscopusnitidulus) (mangoleafhopper), small brown rice planthopper (Laodelphaxstriatellus) (smallerbrownplanthopper), lepidosaphes shimer kind (Lepidosaphesspp.), long tube Aphis kind (Macrosiphumspp.), root of Beijing euphorbia Macrosiphus spp (Macrosiphumeuphorbiae) (potato aphid (potatoaphid)), grain aphid (Macrosiphumgranarium) (Britain's wheat aphid (Englishgrainaphid)), rose aphid (Macrosiphumrosae) (rose aphid (roseaphid)), four line leafhopper (Macrostelesquadrilineatus) (Aster tataricus leafhopper (asterleafhopper)), Mahanarvafrimbiolata, Acyrthosiphon dirhodum (Metopolophiumdirhodum) (rose wheat aphid (rosegrainaphid)), Midislongicornis, black peach aphid (Myzuspersicae) (black peach aphid (greenpeachaphid)), rice green leafhopper belongs to kind of (Nephotettixspp.) (leafhopper), rice green leafhopper (Nephotettixcinctipes) (greenery cicada (greenleafhopper)), brown paddy plant hopper (Nilaparvatalugens) (brownplanthopper), chaff sheet armored scale (Parlatoriapergandii) (chaffscale), ebony armored scale (Parlatoriaziziphi) (ebonyscale), popcorn wing plant hopper (Peregrinusmaidis) (corndelphacid), froghopper belongs to kind of (Philaenusspp.) (spittle insects), grape phylloxera (Phylloxeravitifoliae) (grapephylloxera), Physokermes piceae (Physokermespiceae) (sprucebudscale), stern line mealybug belongs to kind of (Planococcusspp.) (mealybug), mealybug belongs to kind of (Pseudococcusspp.) (mealybug), the clean mealybug of pineapple (Pscudococcusbrcvipcs) (pincapplemcalybug), theatre armored scale (Quadraspidiotusperniciosus) (san jose scale (SanJosescale)), aphid a red-spotted lizard belongs to kind of (Rhapalosiphumspp.) (aphid), corn tree louse (Rhapalosiphummaida) (corn leaf aphids (cornleafaphid)), rhopalosiphum padi (Rhapalosiphumpadi) (oatbird-cherryaphid), pearl lecanium belongs to kind of (Saissetiaspp.) (a red-spotted lizard), olive pearl lecanium (Saissetiaoleae) (black a red-spotted lizard), green bugs (Schizaphisgraminum) (green bugs (greenbug)), grain aphid (Sitobionavenge) (Britain's wheat aphid), white backed planthopper (Sogatellafurcifera) (white-backedplanthopper), variegation Aphis kind (Therioaphisspp.) (aphid), line lecanium belongs to kind of (Toumeyellaspp.) (a red-spotted lizard), sound Aphis kind (Toxopteraspp.) (aphid), trialeurodes vaporariorum belongs to kind of (Trialeurodesspp.) (aleyrodid), Trialeurodes vaporariorum Westwood (Trialeurodesvaporariorum) (greenhouse whitefly (greenhousewhitefly)), knot wing trialeurodes vaporariorum (Trialeurodesabutiloneus) (bandedwingwhitefly), point armored scale belongs to kind of (Unaspisspp.) (a red-spotted lizard), vow sharp clam (Unaspisyanonensis) (arrow a red-spotted lizard (arrowheadscale)) and Zuliaentreriana.
Hymenoptera (Hymenoptera) (ant, wasp and honeybee): Myrmecina kind (Acromyrrmexspp.), Xinjiang cabbage sawfly (Athaliarosae), leaf ant belongs to kind of (Attaspp.) (Ieafcuttingants), black ant belongs to kind of (Camponotusspp.) (carpented ant (carpenterant)), Diprion kind (Diprionspp.) (sawfly (sawfly)), ant belongs to kind of (Formicaspp.) (ant), Argentine ant (Iridomyrmexhumilis) (Argentineant), Monomorium subspecies (Monomoriumssp.), MonomoriumMayr (Monomoriumminumum) (littleblackant), kitchen ant (Monomoriumpharaonis) (little red ant (Pharaohant)), Neodiprion kind (Neodiprionspp.) (sawfly), Pogonomyrmex kind (Pogonomyrmexspp.) (harvester ant), hornet belongs to kind of (Polistesspp.) (wasp (paperwasp)), Solenopsis kind (Solenopsisspp.) (fiery ant), odorous antenna (Tapoinomasessile) (odorous antenna (odoroushouseant)), Tetramorium kind (Tetranomoriumspp.) (Pavement Ant (pavementant)), Vespula kind (Vespulaspp.) (yellow jacket (yellowjacket)) and Xylocopa kind (Xylocopaspp.) (carpenter bee (carpenterbee)).
Isoptera (Isoptera) (termite): formosanes belongs to kind of (Coptotcrmcsspp.), bent jaw termite (Coptotermescurvignathus), France termite (Coptotermesfrenchii), Coptotermes formosanus Shtrari． (Coptotermesformosanus) (Formosansubterraneantermite), angle Cryptotermes kind (Cornitermesspp.) (proboscis termite (nasutetermite)), sand Cryptotermes kind (Cryptotermesspp.) (dry-wood termite), different Cryptotermes kind (Heterotermesspp.) (desert Soil termites (desertsubterraneantermite)), golden yellow different termite ((IIeterotermesaureus), kalotermitid belongs to kind of (Kalotermesspp.) (dry-wood termite), principal columns of a hall Cryptotermes kind (Incistitermesspp.) (dry-wood termite), Macrotermes kind (Macrotermesspp.) (cultivation termite (fungusgrowingtermite)), edge kalotermitid belongs to kind of ((Marginitermesspp.) (dry-wood termite), saw Cryptotermes kind (Microcerotermesspp.) (careless termite (harvestertermite)), the little termite of rice wheat (Microtermesobesi), former angle Cryptotermes kind (Procornitermesspp.), Reticulitermes kind (Reticulitermesspp.) (Soil termites), Reticulitermesbanyulensis, meadow reticulitermes flavipe (Reticulitermesgrassei), yellow limb reticulitermes flavipe (Reticulitermesflavipes) (east Soil termites), beautiful little Huang reticulitermes flavipe (Reticulitermeshageni), west reticulitermes flavipe (Reticulitermeshesperus) (west Soil termites), Sang Te reticulitermes flavipe (Reticulitermessantonensis), dwell northern reticulitermes flavipe (Reticulitermessperatus), U.S. black shin reticulitermes flavipe (Reticulitermestibialis), U.S. little black reticulitermes flavipe (Reticulitermesvirginicus), proboscis Reticulitermes kind (Schedorhinotermesspp.) and ancient Cryptotermes kind (Zootermopsisspp.) (rotten kalotermitid).
Lepidopteran (Lepidoptera) (moth and butterfly): Achoeajanata, Adoxophyes spp belongs to kind of (Adoxophyesspp.), adoxophyes moth (Adoxophyesorana), tiger belongs to kind of (Agrotisspp.) (cutworm) on ground, little cutworm ((Agrotisipsilon) (black cutworm), cotton leaf ripple noctuid (Alabamaargillacea) (cotton leafworm (cottonleafworm)), Amorbiacuneana, Amyelosistransitella (navelorangeworm), Anacamptodesdefectaria, sliver gelechiid (Anarsialineatella) (peachtwigborer), jute bridge night high (Anomissabulijera) (jutelooper), Anticarsia (Anticarsiagemmatalis) (velvetbeancaterpillar), fruittree leafroller (Archipsargyrospila) (fruittreeleafroller), rose leaf roller (Archipsrosana) (roseleafroller), volume moth belongs to kind of (Argyrotaeniaspp.) (tortricidmoths), tangerine Argyrotaenia spp (Argyrotaeniacitrana) (citrus leaf-roller (orangetortrix)), Autographagamma, Bonagotacranaodcs, Cnaphalocrocis medinali(rice leaf roller) (Borbocinnara) (riceleaffolder), cotton leaf lyonetid (Bucculatrixthurberiella) (cottonleafperforator), thin moth belongs to kind of (Caloptiliaspp.) (leaf miner), Capuareticulana, peach fruit moth (Carposinaniponensis) (peach fruit moth (peachfruitmoth)), straw borer spp kind (Chilospp.), Chlumetia transversa Walker (Chlumetiatransversa) (mangoshootborer), rose Choristoneura spp (Choristoneurarosaceana) (obliquebandedleafroller), Noctua kind (Chrysodeixisspp.), cnaphalocrocis medinalls guenee (Cnaphalocerusmedinalis) (meadow leaf roller (grassleafroller)), beans Pier kind (Coliasspp.), lichee litchi (Conpomorphacramerella), the wooden stupid moth (Cossuscossus) of fragrance (wooden stupid moth), Crambus Fabricius kind (Crambusspp.) (Sodwebworms), Lee's small kernel-eating insect (Cydiafunebrana) (Li Guoe (plumfruitmoth)), oriental fruit months (Cydiamolesta) (east heart-eating worm (orientalfruitmoth)), pea moth pod high (Cydianignicana) (peamoth), the stupid moth of apple (Cydiapomonella) (codling moth (codlingmoth)), Darnadiducta, Diaphania kind (Diaphaniaspp.) (stem borer (stemborer)), snout moth's larva belongs to kind of (Diatraeaspp.) (stem borer (stalkborer)), little sugarcane borer (Diatraeasaccharalis) (sugarcaneborer), Diatraea grandiosella (Diatraeagraniosella) (southwestercornborer), Earias kind (Eariasspp.) (bollworm), earias insulana (Eariasinsulata) (Egyptianbollworm), earias fabia (Eariasvit.ella) (roughnorthernbollworm), Ecdytopophaaurantianum, South America maize seedling phycitid (Elasmopalpuslignosellus) (lessercornstalkborer), shallow brown apple moth (Epiphysiaspostruttana) (lightbrownapplemoth), meal moth belongs to kind of (Ephestiaspp.) (a powder snout moth's larva), meal moth (Ephestiacautella) (almondmoth), tobacco powder sp (Ephestiaelutella) (tobacco snout moth's larva (tobbacomoth)), Mediterranean flour moth (Ephestiakuehniella) (Mediterraneanflourmoth), Epimeces belongs to kind of (Epimecesspp.), steinernema at night (Epinotiaaporema), Skipper of plantains (Erionotathrax) (bananaskipper), ligustrum fine tortricidae (Eupoeciliaambiguella) (grape berry moth (grapeberrymoth)), former cutworm (Euxoaauxiliaris) (armycutworm), Agrotis kind (Feltiaspp.) (cutworm), angle sword Noctua kind (Gortynaspp.) (stem borer), east moth fruit moth (Grapholitamolesta) (peach (apricot) sub-heart-eating worm (orientalfruitmoth)), treble cut snout moth (Hedyleptaindicata) (bean pyralid (beanleafwebber)), blue or green Eimeria kind (Helicoverpaspp.) (noctuid), bollworm (Helicoverpaarmigera) (cottonbollworm), paddy real noctuid (Helicoverpazea) (Pyrausta nubilalis (Hubern). ridge (snout moth's larva ridge worm/bollworm)), Heliothis kind (Heliothisspp.) (noctuid), Heliothis virescens (Heliothisvirescens) (tobaccobudworm), Hellula undalis (Hellulaundalis) (cabbagewebworm), Indarbela belongs to kind of (Indarbelaspp.) (a root moth), the stupid moth of tomato (Keiferialycopersicella) (tomatopinworm), the white wing of eggplant wild snout moth's larva (Leucinodesorbonalis) (eggplantfruitborer), pear leaf blister moth (Leucopteramalifoliella), thin moth belongs to kind of (Lithocollectisspp.), grape olethreutid (Lobesiabotrana) (grapefruitmoth), Loxagrotis belongs to kind of (Loxagrotisspp.) (noctuid), beans white line cutworm (Loxagrotisalbicosta) (westernbeancutworm), gypsymoth (Lymantriadispar) (gypsymoth), apple leaf miner (Lyonetiaclerkella) (apple leaf miner (appleleafminer)), oil palm bag moth (Mahasenacorbetti) (oilpalmbagworm), Malacosoma kind (Malacosomaspp.) (tentcaterpillars), lopper worm (Mamestrabrassicae) (dish march moth (cabbagearmyworm)), the wild snout moth's larva (Marucatestulalis) of beanpod (the wild snout moth's larva of beans), bag moth (Metisaplana) (bagworm), Mythimnaunipuncta (truearmyworm), Neoleucinodeselegantalis (little tomato moth (smalltomatoborer)), 3 water snout moth's larvas (Nymphuladepunctalis) (Cnaphalocrocis medinali(rice leaf roller) (ricecaseworm)), winter looper (Operophtherabrumata) (wintermoth), European corn borer (Ostrinianubilalis) (European corn borer (Europeancornborer)), Oxydiavesulia, the brown volume moth (Pandemiscerasana) of boundary (common glucose leaf roller (commoncurranttortrix)), apple brown bortrix (Pandemisheparana) (brownappletortrix), Africa Bodhidharma swallowtail butterfly (Papiliodemodocus), Pectinophora gossypiella (Pectinophoragossypiella) (pink bollworm (pinkbollworm)), boundary Noctua kind (Peridromaspp.) (cutworm), variegated cutworm (Peridromasaucia) (variegatedcutworm), coffee leafminer (Perileucopteracoffeella) (whitecoffeeleafminer), phthorimaea operculella (Phthorimaeaoperculella) (potatotubermoth), citrus leaf lyonetid (Phyllocnisitiscitrella), thin moth belongs to kind of (Phyllonorycterspp.) (leaf miner), small white (Pierisrapae) (external cabbage caterpillar (importedcabbageworm)), the first green noctuid of mat (Plathypenascabra), India paddy spot moth (Plodiainterpunctella) (Indianmealmoth), diamond-back moth (Plutellaxylostella) (diamondbackmoth), grape berry moth (Polychrosisviteana) (grapeberrymoth), tangerine fruit ermine moth (Praysendocarps), Fructus oleae europaeae ermine moth (Prsysoleae) (olivemoth), mythimna separata belongs to kind of (Pseudaletiaspp.) (noctuid), Pseudaletiaunipunctata (armyworm), soybean noctuid (Pseudoplusiaincludens) (soybeanlooper), looper (Rachiplusianu), yellow rice borer (Scirpophagaincertulas), moth stem night, high genus planted (Sesamiaspp.) (stem borer), Sesamia inferens (Sesamiainferens) (pinkricestemborer), powder stem snout moth's larva (Sesamianonagrioides), the brown slug moth of copper stain (Setoranitens), gelechiid (Sitotrogacerealella) (Angoumoisgrainmoth), pilleriana (Sparganothispilleriana), Spodoptera kind (Spodopteraspp.) (armyworm), beet armyworm (Spodopteraexigua) (beet armyworm (beetarmyworm)), noctuid (Spodoptcrafugipcrda) (armyworm in autumn (fallarmyworm)) is coveted on meadow, south spodoptera (Spodopteraoridania) (southern armyworm (southernarmyworm)), emerging Noctua kind (Synanthedonspp.) (root moth), Theclabasilides, Thermisiagemmatalis, casemaking clothes moth (Tineolabisselliella) (webbingclothesmoth), cabbage looper (Trichoplusiani) (cabbagelooper), Liriomyza brponiae (Tutsabsoluta), Yponomeuta kind (Yponomeutaspp.), the stupid moth of coffee leopard (Zeuzeracoffeae) (redbranchborer) and Zeuzerapyrina (the stupid moth of pears leopard (leopardmoth)).
Mallophaga ((Mallophaga) poultry louse (chewinglice)): sheep poultry louse (Bovicolaovis) (sheepbitinglouse), fiery menopon gallinae (Menacanthusstramineus) (chick poultry louse (chickenbodylouse)) and shaft louse (Menopongallinea) (common hen house (commonhenhouse)).
Orthoptera (Orthoptera) (grasshopper, locust and cricket): blackspot arna Zhong (Anabrussimplex) (rub a katydid (Mormoncricket)), mole cricket (Gryllotalpidae) (mole cricket (molecricket)), Asiatic migrotory locust (Locustamigratoria), grasshopper belongs to kind of (Melanoplusspp.) (grasshopper), guiding principle wing spinelet Zhong (Microcentrumretinerve) (angle wing katydid (angularwingedkatydid)), Pterophylla belongs to kind of (Pterophyllaspp.) (katydid), chistocercagregaria, fork-tail katydid (Scudderiafurcata) (fork-tail shrubbery tree Zhong (forktailedbushkatydid)) and black angle oncus locust (Valanganigricorni).
Anoplura (Phthiraptera) (sucking lice (suckinglouse)): sucking louse belongs to kind of (Haematopinusspp.) (ox louse and a pig lice), sheep jaw lice (Linognathusovillus) (sheep lice (sheeplouse)), head louse (Pediculushumanuscapitis) (body louse), pediculus humanus corporis (Pediculushumanushumanus) (body louse) and crab louse (Pthiruspubis) (crab louse (crablouse)).
Siphonaptera (Siphonaptera) (flea): ctenocephalides canis (Ctenocephalidescanis) (dogflea), ctenocephalides felis (Ctenocephalidesfelis) (catflea) and Pulex irritans (Pulexirritans) (humanflea).
Thysanoptera (thrips): cigarette brown thrip (Frankliniellafusca) (tobaccothrip), western classical architecture (Frankliniellaoccidentalis) (westernflowerthrips), Frankliniellashultzei, Williams flower thrips (Frankliniellawilliamsi) (corn thrips (cornthrip)), greenhouse thrips (IIeliothripshaemorrhaidalis) (greenhousethrip), Riphiphorothripscruentatus, hard Thrips kind (Scirtothripsspp), balloonflower root thrips (Scirtothripscirri) (citrusthrip), Scirothrips dorsalis (Scirtothripsdorsalis) (yellowteathrips), Taeniothripsrhopalantennalis and Thrips kind (Thripsspp.).
Thysanura (Thysanura) (moth (bristletail)): silverfish belongs to kind of (Lepismaspp.) (stupid worm (silverfish)) and special mess silverfish belongs to kind of (Thermobiaspp.) (a special mess fish).
Acarina (Acarina) (mite (mite) and cicada (tick)): Wu Shi honeybee shield mite (Acarapsiswoodi) (honeybee Tracheal mite (trachealmiteofhoneybee)), Tyroglyphus kind (Acarusspp.) (food mites), Acarus siro (Acarussiro) (paddy mite (grainmite)), mango bud mite (Aceriamangiferae) (mangobudmite), peronium Eriophyes kind (Aculopsspp.), Aculops lycopersici (Aculopslycopersici) (tomatorussetmite), Aculopspelekasi, tangerine peronium goitre mite (Aculuspelekassi), Si Shi stings goitre mite (Aculusschlechtendali) (apple thorn goitre mite (applerustmite)), lone star tick (Amblyommaamcricanum) (lonestartick), Boophilus kind (Boophilusspp.) (tick), avette short hairs tick (Brevipalpusobovatus) (privetmite), purplish red short hairs mite (Brevipalpusphoenicis) (redandblackflatmite), fat tick belongs to kind of (Demodexspp.) (mangemites), Dermacentor kind (Dermacentorspp.) (hard tick), America dog tick (Dermacentorvariabilis) (americandogtick), dermatophagoides pteronyssinus (Dermatophagoidespteronyssinus) (housedustmite), Eotetranychus kind (Eotetranycusspp.), Eotetranychus carpini (Eotetranychuscarpini) (yellow spider mite (yellowspidermite)), Epitrimerus kind (Epitimerusspp.), Eriophyes kind (Eriophyesspp.), hard tick belongs to kind an of (work, odesspp.) (tick), Panonychus citri belongs to kind of ((Metatetranycusspp.), notoedres cati (Notoedrescati), Oligonychus kind (Oligonychusspp.), coffee unguiculus mite (Oligonychuscoffee), ilex Oligonychus (Oligonychusilicus) (southernredmite), Panonychus citri belongs to kind of (Panonychusspp.), Jie-Li enzyme-SQ (Panonychuscirri) (orange spider (citrusredmite)), panonychus ulmi (Panonychusulmi) (European red spider (Europeanredmite)), tangerine wrinkle leaf thorn goitre (Phyllocoptrutaoleivora) (citrusrustmite), Polyphagotarsonemus latus Banks (Polyphagotarsonemunlatus) (broad mite (broadmite)), brown dog tick (Rhipicephalussanguineus) (brown dog tick (browndogtick)), root mite belongs to kind of (Rhizoglyphusspp.) (root mite (bulbmite)), itch mite (Sarcoptesscabiei) (itchmite), avocado apical cap goitre mite (Tegolophusperseaflorae), Tetranychus kind (Tetranychusspp.), T.urticae Koch (Tetranychusurticae) (2 spider mites (twospottedspidermite)) and Di Shi watt of mite (Varroadestructor) (honeybee mite).
Nematoda (nematode): Aphelenchoides kind (Aphelenchoidesspp.) (bud and leaf and pine wood nematode (budandleaf & pinewoodnematode)), thorn Turbatrix kind (Belonolaimusspp.) (stingnematodes), little loop wire Eimeria kind (Criconemellaspp.) (ringnematodes), heart worm (Dirofilariaimmitis) (dogheartworm), Ditylenchus kind (Ditylenchusspp.) (stem and bulb eelworm), sour jujube rubber-insulated wire Eimeria kind (Heteroderaspp.) (cystnematode), corn Cyst nematode (Heteroderazeae) (corncystnematode), Hirschmanniella kind (Hirschmanniellaspp.) (rootnematodes), tie Turbatrix kind (Hoplolaimusspp.) (lancenematodes), Meloidogyne kind (Meloidogynespp.) (root knot nematode), Meloidogyne incognita ((Meloidogyneincognita) (root knot nematode), Onchocerca caecutiens (Onchocercavolvulus) (hook-tailworm), Pratylenchidae belongs to kind of (PraLylenchusspp.) (rotten nematode (lesionnematode)), perforation line Eimeria kind (Radopholusspp.) (similes thorne (burrowingnematode)) and banana reniform nematode (Rotylenchusreniformis) (kidney-shapednematode).
Symphyla (comprehensive insects): kahikatea worm (Scutigerellaimmaculata).
Especially, to small cabbage moth, mythimna separata, aphid, carmine spider mite, at lower doses still there is good prevention effect.
Due to the characteristic that it is positive, above-claimed cpd can be advantageously used in protecting agriculture and the important crop of horticulture, domestic animal and breeding stock, and the environment that often goes of the mankind avoids the injury of germ, insect evil mite.
For obtaining ideal effect, the consumption of compound changes because of various factors, the formulation of the crop of such as compound used therefor, pre-protection, the type of harmful organism, gradient of infection, weather condition, application method, employing.
The compound dosage of per hectare 10 grams-5 kilograms can provide sufficient control.
The present invention also comprises sterilization using compound of Formula I as active ingredient, insecticide acaricide composition.In this sterilization, insecticide acaricide composition, the weight percentage of active ingredient is between 0.5-99%.Acceptable carrier in agricultural, forestry, health is also comprised in this sterilization, insecticide acaricide composition.
Composition of the present invention can the form of preparation be used.Compound of Formula I is dissolved or dispersed in carrier as active ingredient or is mixed with preparation to be easier to dispersion as sterilization, desinsection when using.Such as: these chemicals can be made into wettable powder, oil suspending agent, aqueous suspension, aqueous emulsion, aqua or missible oil etc.In these compositions, at least add a kind of liquid or solid carrier, and suitable tensio-active agent can be added when needed.
Technical scheme of the present invention also comprises the method for control germ, insect evil mite: sterilization of the present invention, insecticide acaricide composition are imposed on described germ or its growth medium.The comparatively suitable effective amount of usual selection is per hectare 10 grams to 1000 grams, and preferably having effective amount is per hectare 20 grams to 500 grams.
For some application, such as, one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc. agriculturally can be added in sterilization of the present invention, insecticide acaricide composition, additional advantage and effect can be produced thus.
Should it is clear that, in claim limited range of the present invention, can various conversion and change be carried out.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.(except as otherwise indicate outside, raw materials used all have commercially available)
Synthetic example
Embodiment 1: the preparation of the chloro-6-methylpyrimidine of intermediate 4,5-bis-
1) preparation of the chloro-6-methylpyrimidine of 4-hydroxyl-5-
To 11.30g(0.11mol under stirring at room temperature) 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, 11.17g(0.068mol is dripped) intermediate 2-chloroacetyl acetacetic ester, continue stirring at room temperature reaction 5-7 hour, TLC monitoring after completion of the reaction, remove solvent under reduced pressure, pH=5 ~ 6 are adjusted with hydrochloric acid, suction filtration obtains orange/yellow solid, aqueous phase (3 × 50ml) extraction into ethyl acetate, anhydrous magnesium sulfate drying, filtration, precipitation.Resistates is dissolved in 50ml ethyl acetate, and placement is spent the night, and filters to obtain orange/yellow solid 6.48g.Yield 66%, fusing point 181 ~ 184 DEG C.
2) preparation of the chloro-6-methylpyrimidine of the chloro-5-of 4-
By 14.5g(0.1mol) the chloro-6-methylpyrimidine of 4-hydroxyl-5-is dissolved in 50ml toluene solution, instills 50ml phosphorus oxychloride under stirring in anti-bottle, drips the reaction of a complete temperature rising reflux 5-7 hour, TLC monitoring after completion of the reaction.Remove toluene and excessive phosphorus oxychloride under reduced pressure, by reactant impouring frozen water under stirring, aqueous phase (3 × 50ml) extraction into ethyl acetate, merges organic phase, anhydrous magnesium sulfate drying, filtration, precipitation.Resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1:4) is separated to obtain yellow liquid 14.43g, yield 88.5%.
Embodiment 2: the preparation of the chloro-6-difluoromethyl pyrimidin of intermediate 4,5-bis-
1) preparation of the chloro-6-difluoromethyl pyrimidin of 4-hydroxyl-5-
Get 71.9g(0.70mol) FORMAMIDINE ACETATE is in the there-necked flask of 1000ml, add 150ml methyl alcohol, in 5-10 DEG C of stirring, then by pre-configured and be chilled to room temperature containing 64.6g(1.20mol) methanol solution of 30% sodium methylate of sodium methylate, pour in reaction flask, 100g(0.50mol is added again in reaction mixture) the 100ml methanol solution of chloro-4, the 4-difluoro methyl aceto acetates of 2-.Reaction mixture continues stirring reaction 3 ~ 4 hours.After completion of the reaction, remove solvent under reduced pressure, adjust pH=5 ~ 6 with hydrochloric acid, suction filtration obtains white solid 65g in TLC monitoring.Yield 73%, fusing point 204 ~ 206 DEG C.
2) preparation of 4,5-bis-chloro-6-difluoromethyl pyrimidin
By 65.0g(0.36mol) the chloro-6-difluoromethyl pyrimidin of 4-hydroxyl-5-is dissolved in 150ml toluene solution, instills 100ml phosphorus oxychloride under stirring in anti-bottle, drips complete temperature rising reflux 3-5 hour.TLC monitoring after completion of the reaction, removes toluene and excessive phosphorus oxychloride under reduced pressure, by residue impouring frozen water under stirring, aqueous phase (3 × 50ml) extraction into ethyl acetate, merge organic phase, with saturated sodium bicarbonate solution washing to neutral, anhydrous magnesium sulfate drying, filtration, precipitation.Resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1:4) is separated to obtain yellow liquid 64.5g, is placed in refrigerator and is frozen into solid, yield 90%.
Embodiment 3: the preparation of intermediate 2-(6-(4-chlorophenoxy) pyridin-3-yl) ethamine
1) preparation of 6-(4-chlorophenoxy) nicotinic acid methyl ester
To the 350mlN of 25.6g (0.2mol) para-chlorophenol, in dinethylformamide solution, add the sodium hydride 103g (3.0mol) of 70% in batches, in stirring at room temperature reaction 4h, then add 34.2g (0.2mol) 6-chlorine apellagrin methyl esters wherein in batches, finish, reaction mixture is warming up to 100 DEG C of reaction 10h, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, after resistates cooled and solidified, filter, petroleum ether, brown solid 42.0g is obtained after drying, i.e. 6-(4-chlorophenoxy) nicotinic acid methyl ester.Fusing point: 64-66 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 3.92 (3H, s), 6.75 (1H, d), 6.96 (1H, d), 7.11 (2H, d), 7.37 (2H, d), 8.30 (1H, d), 8.81 (1H, s).
2) preparation of (6-(4-chlorophenoxy) pyridin-3-yl) methyl alcohol
At 0 DEG C, to in the 500ml anhydrous ether solution of 52.6g (0.2mol) 6-(4-chlorophenoxy) nicotinic acid methyl ester, drip the red aluminium toluene solution 74.5g (0.24mol) of 65%, finish, in stirring at room temperature reaction 4h, then at 0 DEG C, drip 10% sodium hydroxide solution prepared in advance wherein, until reaction mixture becomes clarification, then 35 DEG C of reaction 2h are warming up to, TLC monitoring after completion of the reaction, reaction solution is poured into water, toluene extracts, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:3) purifying obtains product 42.2g, i.e. (6-(4-chlorophenoxy) pyridin-3-yl) methyl alcohol.White solid.Fusing point: 100-102 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 3.20 (1H, bs), 4.56 (2H, s), 6.87 (1H, d), 7.04 (2H, d), 7.33 (2H, d), 7.69 (1H, d), 8.06 (1H, s).
3) preparation of 5-chloromethyl-2-(4-chlorophenoxy) pyridine
At 0 DEG C, to in the 350ml dichloromethane solution of 23.5g (0.1mol) (6-(4-chlorophenoxy) pyridin-3-yl) methyl alcohol, drip 17.9g (0.15mol) sulfur oxychloride, finish, in stirring at room temperature reaction 4h, TLC monitoring after completion of the reaction, decompression steams excessive sulfur oxychloride, resistates adds water, extraction into ethyl acetate, organic phase is successively through washing, and saturated sodium bicarbonate is washed, saturated salt is washed, drying, filters, precipitation, obtain product 22.8g, i.e. 5-chloromethyl-2-(4-chlorophenoxy) pyridine.White solid.Fusing point: 78-80 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 4.55 (2H, s), 6.94 (1H, d), 7.09 (2H, d), 7.36 (2H, d), 7.75 (1H, d), 8.15 (1H, s).
4) preparation of 2-(6-(4-chlorophenoxy) pyridin-3-yl) acetonitrile
At 40 DEG C, 2.69g (55mmol) sodium cyanide is dissolved in 300ml dimethyl sulfoxide (DMSO), then 13.9g (50mmol) 5-chloromethyl-2-(4-chlorophenoxy) pyridine is added wherein, add the 18-hat-6 of catalytic amount, reaction mixture is warming up to 80 DEG C of reaction 2h, TLC monitoring after completion of the reaction, reaction solution is poured into water, toluene extracts, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:3) purifying obtains product 11.2g, i.e. 2-(6-(4-chlorophenoxy) pyridin-3-yl) acetonitrile.White solid.Fusing point: 100-102 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 3.70 (2H, s), 6.97 (1H, d), 7.08 (2H, d), 7.37 (2H, d), 7.71 (1H, d), 8.10 (1H, s).
5) 2-(preparation of 6-(4-chlorophenoxy pyridin-3-yl) ethamine
By 2.44g(0.01mol) 2-(6-(4-chlorophenoxy) pyridin-3-yl) acetonitrile, Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml composition mixture hydrogen atmosphere, stirred at ambient temperature reaction 3-15 hour, TLC monitoring after completion of the reaction, filtering Raney nickel, remove solvent under reduced pressure and obtain pale green viscous shape liquid 2.30g, yield 95.0%.Colorless oil.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ ppm1.46 (2H, bs), 2.70 (2H, t), 2.94 (2H, t), 6.87 (1H, d), 7.07 (2H, dd), 7.34 (2H, dd), 7.55 (1H, dd), 8.02 (1H, d).
Embodiment 4: the preparation of compound 7
To the 10mlN of 0.25g (10mmol) 2-(6-(4-chlorophenoxy) pyridin-3-yl) ethamine, in dinethylformamide solution, add salt of wormwood 0.21g (1.5mmol), 4 are added under stirring, 5-bis-chloro-6-methylpyrimidine 0.16g (1.0mmol), 80 DEG C of reaction 2h are warming up to after adding, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:4) purifying obtains product 0.28g, i.e. compound 7.Colorless oil.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 2.46 (3H, t), 2.91 (2H, t), 3.75 (2H, m), 5.43 (1H, bs), 6.89 (1H, d), 7.07 (2H, d), 7.35 (2H, d), 7.58 (1H, dd), 8.03 (1H, d), 8.39 (1H, s).
Embodiment 5: the preparation of compound 202
To 0.28g (1.0mmol) 2-(6-(4-4-trifluoromethylphenopendant) pyridin-3-yl) ethamine (preparation method's reference as above embodiment 3, difference is that starting raw material para-chlorophenol is replaced with p-trifluoromethyl-phenol) 10mlN, in dinethylformamide solution, add salt of wormwood 0.21g (1.5mmol), 4 are added under stirring, 5-bis-chloro-6-ethyl-pyrimidine 0.18g (1.0mmol) (preparation method's reference as above embodiment 1, difference is that starting raw material 2-chloroacetyl acetacetic ester is replaced with 2-chlorine Propionylacetic acid ethyl ester), 80 DEG C of reaction 2h are warming up to after adding, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:4) purifying obtains product 0.30g, i.e. compound 202.Colorless oil.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 1.28 (3H, t), 2.78 (2H, m), 2.93 (2H, t), 3.76 (2H, m), 5.43 (1H, bs), 6.96 (1H, d), 7.20-7.23 (2H, m), 7.61-7.66 (3H, m), 8.06 (1H, d), 8.44 (1H, s).
Embodiment 6: the preparation of compound 622
To 0.28g (1.0mmol) 2-(6-(2, 4-dichlorophenoxy) pyridin-3-yl) ethamine (preparation method's reference as above embodiment 3, difference is that starting raw material para-chlorophenol is replaced with 2, 4-chlorophenesic acid) 10mlN, in dinethylformamide solution, add salt of wormwood 0.21g (1.5mmol), 4 are added under stirring, 5-bis-chloro-6-difluoromethyl pyrimidin 0.20g (1.0mmol), 80 DEG C of reaction 2h are warming up to after adding, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:4) purifying obtains product 0.32g, i.e. compound 622.Colorless oil.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 2.92 (2H, t), 3.80 (2H, m), 5.72 (1H, bs), 6.54,6.72,6.90 (1H, t), 6.89 (1H, s), 6.98 (1H, d), 7.14 (1H, d), 7.27-7.31 (2H, m), 7.48 (1H, d), 7.61 (1H, dd), 7.98 (1H, d), 8.56 (1H, s).
Embodiment 7: the preparation of compound 2630
To 0.26g (1.0mmol) 2-(6-(2-methyl-4-chlorophenoxy) pyridin-3-yl) ethamine (preparation method's reference as above embodiment 3, difference starting raw material para-chlorophenol is replaced with 2-methyl-4-chlorophenol) 10mlN, in dinethylformamide solution, add salt of wormwood 0.21g (1.5mmol), 4 are added under stirring, 5, 6-trichloropyrimidine 0.18g (1.0mmol) (preparation method's reference as above embodiment 1, difference is that starting raw material 2-chloroacetyl acetacetic ester is replaced with 2-chlorine diethyl malonate), 80 DEG C of reaction 2h are warming up to after adding, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:4) purifying obtains product 0.32g, i.e. compound 2630.Colorless oil.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 2.15 (3H, s), 2.89 (2H, t), 3.73-3.79 (2H, m), 5.62 (1H, bs), 6.87 (1H, d), 6.98 (1H, d), 7.18-7.22 (2H, m), 7.54 (1H, dd), 8.00 (1H, d), 8.29 (1H, s).
Other compounds of the present invention can be prepared with reference to above embodiment.
The physical data of part of compounds and nuclear magnetic data (
1hNMR, 300MHz, interior mark TMS, ppm) as follows:
Compound 1: colorless oil.δ(CDCl
3):2.50(3H,s),2.88(2H,t),3.74(2H,m),5.45(1H,bs),6.87(1H,d),7.09-7.22(3H,m),7.36-7.42(2H,m),7.56(1H,dd),8.05(1H,d),8.38(1H,s)。
Compound 5: colorless oil.
Compound 6: colorless oil.δ(CDCl
3):2.46(3H,s),2.92(2H,t),3.75(2H,m),5.42(1H,bs),6.90(1H,d),7.03(1H,dd),7.13-7.18(2H,m),7.29(1H,d),7.59(1H,dd),8.05(1H,d),8.39(1H,s)。
Compound 16: colorless oil.δ(CDCl
3):2.35(3H,s),2.52(3H,s),2.88(2H,t),3.70-3.77(2H,m),5.42(1H,bs),6.85(1H,d),7.01(2H,d),7.19(2H,d),7.53(1H,dd),8.03(1H,d),8.38(1H,s)。
Compound 19: colorless oil.δ(CDCl
3):2.46(3H,s),2.89(2H,t),3.70-3.77(2H,m),3.82(3H,s),5.42(1H,bs),6.83(1H,d),6.92(2H,d),7.06(2H,d),7.53(1H,dd),8.03(1H,d),8.38(1H,s)。
Compound 21: colorless oil.
Compound 22: colorless oil.δ(CDCl
3):2.46(3H,t),2.93(2H,t),3.76(2H,m),5.43(1H,bs),6.95(1H,d),7.20-7.28(2H,m),7.60-7.66(3H,m),8.06(1H,d),8.39(1H,s)。
Compound 82: colorless oil.δ(CDCl
3):2.46(3H,s),2.90(2H,t),3.74(2H,m),5.42(1H,bs),6.97(1H,d),7.14(1H,d),7.28(1H,d),7.49(1H,d),7.62(1H,dd),7.97(1H,d),8.38(1H,s)。
Compound 83: colorless oil.δ(CDCl
3):2.46(3H,s),2.91(2H,t),3.75(2H,m),5.42(1H,bs),6.97(1H,d),7.16(1H,dd),7.22(1H,d),7.40(1H,d),7.61(1H,dd),7.99(1H,d),8.39(1H,s)。
Compound 110: colorless oil.δ(CDCl
3):2.14(3H,t),2.46(3H,t),2.89(2H,t),3.73(2H,m),5.42(1H,bs),6.86(1H,d),6.97(1H,d),7.17-7.25(2H,m),7.56(1H,dd),7.99(1H,d),8.38(1H,s)。
Compound 181: colorless oil.δ(CDCl
3):1.26(3H,t),2.78(2H,m),2.90(2H,t),3.75(2H,m),5.45(1H,bs),6.87(1H,d),7.11-7.22(3H,m),7.36-7.42(2H,m),7.56(1H,dd),8.05(1H,d),8.43(1H,s)。
Compound 185: colorless oil.δ(CDCl
3):1.26(3H,t),2.78(2H,m),2.88(2H,t),3.74(2H,m),5.43(1H,bs),6.94(1H,d),7.20(2H,d),7.28-7.32(1H,m),7.47(1H,d),7.59(1H,dd),8.00(1H,d),8.43(1H,s)。
Compound 186: colorless oil.δ(CDCl
3):1.26(3H,t),2.75-2.83(2H,m),2.89-2.96(2H,m),3.72-3.79(2H,m),5.47(1H,bs),6.91(1H,d),7.03(1H,d),7.13-7.19(2H,m),7.29-7.34(1H,m),7.60(1H,dd),8.06(1H,s),8.44(1H,s)。
Compound 187: colorless oil.δ(CDCl
3):1.26(3H,t),2.79(2H,m),2.91(2H,t),3.75(2H,m),5.43(1H,bs),6.89(1H,d),7.07(2H,d),7.35(2H,d),7.58(1H,dd),8.03(1H,dd),8.43(1H,s)。
Compound 196: colorless oil.δ(CDCl
3):1.23(3H,t),2.35(3H,s),2.74-2.91(5H,m),3.70-3.77(2H,m),5.46(1H,bs),6.85(1H,d),6.99(2H,d),7.19(2H,d),7.54(1H,dd),8.03(1H,d),8.43(1H,s)。
Compound 199: colorless oil.δ(CDCl
3):1.26(3H,t),2.75-2.82(2H,m),2.88(2H,t),3.70-3.77(2H,m),3.82(3H,s),5.42(1H,bs),6.83(1H,d),6.92(2H,d),7.06(2H,d),7.54(1H,dd),8.03(1H,d),8.43(1H,s)。
Compound 201: colorless oil.
Compound 262: colorless oil.δ(CDCl
3):1.26(3H,t),2.79(2H,m),2.90(2H,t),3.74(2H,m),5.42(1H,bs),6.97(1H,d),7.14(1H,d),7.29(1H,d),7.48(1H,d),7.61(1H,dd),7.97(1H,d),8.43(1H,s)。
Compound 263: colorless oil.δ(CDCl
3):1.26(3H,t),2.81(2H,m),2.91(2H,t),3.75(2H,m),5.43(1H,bs),6.98(1H,d),7.14-7.22(2H,m),7.40(2H,d),7.63(1H,dd),7.99(1H,s),8.44(1H,s)。
Compound 290: colorless oil.δ(CDCl
3):1.26(3H,t),2.14(3H,s),2.78(2H,m),2.89(2H,t),3.74(2H,m),5.42(1H,bs),6.86(1H,d),6.97(1H,d),7.19(1H,dd),7.25(1H,d),7.57(1H,dd),8.00(1H,d),8.43(1H,s)。
Compound 541: colorless oil.δ(CDCl
3):2.91(2H,t),3.81(2H,m),5.73(1H,bs),6.54,6.71,6.83(1H,t),6.88(1H,d),7.09-7.18(2H,m),7.22(1H,t),7.36-7.42(2H,m),7.56(1H,dd),8.07(1H,d),8.56(1H,s)。
Compound 545: colorless oil.δ(CDCl
3):2.92(2H,t),3.80(2H,m),5.71(1H,bs),6.53,6.71,6.89(1H,t),6.95(1H,d),7.18-7.32(3H,m),7.47(1H,d),7.59(1H,dd),8.00(1H,d),8.56(1H,s)。
Compound 546: colorless oil.δ(CDCl
3):2.94(2H,t),3.77-3.82(2H,m),5.74(1H,bs),6.54,6.72,6.89(1H,t),6.91(1H,d),7.02(1H,d),7.13-7.18(2H,m),7.29-7.35(1H,m),7.61(1H,dd),8.06(1H,d),8.61(1H,s)。
Compound 547: colorless oil.δ(CDCl
3):2.93(2H,t),3.80(2H,m),5.72(1H,bs),6.53,6.72,6.89(1H,t),6.92(1H,d),7.07(2H,d),7.35(2H,d),7.58(1H,dd),8.03(1H,s),8.56(1H,s)。
Compound 556: colorless oil.δ(CDCl
3):2.35(3H,t),2.91(2H,t),3.76-3.84(2H,m),5.73(1H,bs),6.54,6.72,6.84(1H,t),6.89(1H,d),7.01(1H,d),7.19(1H,d),7.55(1H,dd),8.04(1H,d),8.56(1H,s)。
Compound 559: colorless oil.δ(CDCl
3):2.91(2H,t),3.76-3.81(5H,m),5.73(1H,bs),6.54,6.72,6.84(1H,t),6.91(1H,d),6.94(1H,dd),7.06(1H,dd),7.54(1H,dd),8.03(1H,d),8.56(1H,s)。
Compound 561: colorless oil.δ(CDCl
3):2.95(2H,t),3.81(2H,m),5.74(1H,bs),6.54,6.72,6.89(1H,t),6.95(1H,d),7.32(1H,d),7.39(1H,s),7.44-7.54(2H,m),7.62(1H,dd),8.05(1H,d),8.57(1H,s)。
Compound 562: colorless oil.δ(CDCl
3):2.95(2H,t),3.81(2H,m),5.74(1H,bs),6.54,6.72,6.89(1H,t),6.97(1H,d),7.21-7.24(2H,m),7.61-7.67(3H,m),8.06(1H,d),8.57(1H,s)。
Compound 623: colorless oil.δ(CDCl
3):2.92(2H,t),3.80(2H,m),5.72(1H,bs),6.54,6.72,6.89(1H,t),6.91(1H,s),6.99(1H,d),7.15-7.22(2H,m),7.40(1H,d),7.61(1H,dd),8.00(1H,d),8.57(1H,s)。
Compound 650: colorless oil.δ(CDCl
3):2.13(3H,s),2.91(2H,t),3.79(2H,m),5.66(1H,bs),6.53,6.72,6.86(1H,t),6.89(1H,s),6.97(1H,d),7.17-7.25(2H,m),7.57(1H,dd),8.01(1H,d),8.56(1H,s)。
Compound 2521: colorless oil.δ(CDCl
3):2.90(2H,t),3.74-3.81(2H,m),5.60(1H,bs),6.83-6.89(1H,m),7.09-7.11(2H,m),7.13-7.22(1H,m),7.37-7.42(2H,m),7.49-7.56(1H,m),8.15(1H,d),8.29(1H,s)。
Compound 2526: colorless oil.δ(CDCl
3):2.92(2H,t),3.74-3.81(2H,m),5.62(1H,bs),6.91(1H,d),7.02(1H,d),7.14-7.18(2H,m),7.29-7.34(1H,m),7.57-7.60(1H,m),8.05(1H,d),8.32(1H,s)。
Compound 2527: colorless oil.δ(CDCl
3):2.91(2H,t),3.74-3.81(2H,m),5.60(1H,bs),6.90(1H,d),7.07(2H,dd),7.35(2H,dd),7.54(1H,dd),8.03(1H,d),8.29(1H,s)。
Compound 2536: colorless oil.δ(CDCl
3):2.36(3H,s),2.89(2H,t),3.73-3.79(2H,m),5.62(1H,bs),6.85(1H,d),6.98-7.02(2H,m),7.20(2H,d),7.54(1H,dd),8.03(1H,d),8.29(1H,s)。
Compound 2539: colorless oil.δ(CDCl
3):2.89(2H,t),3.73-3.79(2H,m),3.81(3H,t),5.61(1H,bs),6.83(1H,d),6.92(2H,dd),7.05(2H,dd),7.52(1H,dd),8.03(1H,d),8.29(1H,s)。
Compound 2541: colorless oil.δ(CDCl
3):2.93(2H,t),3.75-3.82(2H,m),5.62(1H,bs),6.94(1H,d),7.32(1H,d),7.40-7.51(3H,m),7.60(1H,dd),8.04(1H,d),8.30(1H,s)。
Biological activity determination
The compounds of this invention all shows good activity to the multiple germ in agriculture field, also demonstrates good pesticide and miticide actility.
Embodiment 8: fungicidal activity measures
Antifungal Activity in Vitro or the test of live body protected effect has been carried out with the multiple fungal disease of the compounds of this invention sample to plant.Fungicidal activity measurement result is shown in following example.
(1) Antifungal Activity in Vitro measures
Measuring method is as follows: adopt high-throughput screening method, dissolves, be mixed with desired concn liquid to be measured by the test compound sample solvent (kind of solvent as acetone, methyl alcohol, DMF etc., and is selected the dissolving power of sample according to it) be applicable to.Under ultra-clean Working environment, joined by liquid to be measured in the micropore of 96 well culture plates, then add wherein by pathogenic bacteria propagulum suspension, the culture plate after process is placed in constant incubator to be cultivated.Investigate after 24 hours, estimate pathogenic bacteria propagulum during investigation and sprout or growing state, and according to the sprouting of control treatment or growing state, assessing compound bacteriostatic activity.
Antifungal Activity in Vitro (representing with the inhibiting rate) test result of part of compounds is as follows:
Inhibiting rate to rice blast fungus:
When liquor strength is 25mg/L, the inhibiting rate of compound 7 grade is 100%, and the inhibiting rate of compound 1,5,6,7,16,19,21,22,82,83,110,181,186,187,196,199,201,202,262,541,545,546,547,556,559,561,562,622,623,2521,2526,2536,2539,2541,2630 etc. is 80%; When liquor strength is 8.3mg/L, the inhibiting rate of compound 7 grade is 100%; When liquor strength is 2.8mg/L, the inhibiting rate of compound 7 grade is 100%; When liquor strength is 0.9mg/L, the inhibiting rate of compound 7 grade is 100%; When liquor strength is 0.3mg/L, the inhibiting rate of compound 7 grade is 100%; When liquor strength is 0.1mg/L, the inhibiting rate of compound 7 grade is 100%.
Inhibiting rate to botrytis cinerea pers:
When liquor strength is 25mg/L, the inhibiting rate of compound 82 grade is 100%, and the inhibiting rate of compound 7,199,262,545,547,559,622 etc. is 80%; The inhibiting rate of control compound KC1, KC2, KC3, KC8 is 0; The inhibiting rate of KC6, KC7, KC2 is 50%; The inhibiting rate of KC1, KC2, KC3, KC8, KC12, KC13, KC14, KC15, KC16, KC17, KC18, KC19, KC23, fluorine mepanipyrim and phonetic worm amine is 0; The inhibiting rate of KC6, KC7, KC20 is 50%.
(2) live body prolection measures
Measuring method is as follows: adopt the potted plant measuring method of live body, by test compound sample, with a small amount of solvent, (kind of solvent is as acetone, methyl alcohol, DMF etc., and according to it, dissolving power of sample is selected, the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05) dissolve, dilute with the water containing 0.1% tween 80, be mixed with desired concn liquid to be measured.On crops sprayer, liquid to be measured is sprayed on disease host plant (host plant is the standard Potted orchard at warm indoor cultivation), after 24 hours, carry out disease inoculation.According to disease feature, cultivate being placed in phytotron after the disease plant inoculating needing temperature control moisturizing to cultivate, after disease completes and infects, immigration hot-house culture, the disease plant cultivated not needing moisturizing is directly cultivated at warm indoor inoculation.After contrasting fully morbidity, (being generally week age) carries out the assessment of compound protection effect.
The live body prolection test result of part of compounds is as follows:
Live body preventive effect to cucumber downy mildew:
When liquor strength is 400mg/L, the preventive effect of compound 1,5,7,16,19,22,82,110,181,187,196,199,201,202,262,263,290,541,547,556,562,622,623,650,2521,2526,2527,2536,2539,2541,2630 etc. is 100%;
When liquor strength is 100mg/L, the preventive effect of compound 1,5,7,16,19,22,82,110,181,187,196,199,201,202,262,263,541,547,556,562,622,623,650,2521,2526,2527,2536,2539,2541 etc. all reaches 100%, and the preventive effect of compound 2630 grade is 98%; The preventive effect of compound 290 grade is 80%;
When liquor strength is 50mg/L, the preventive effect of compound 1,5,7,16,19,22,82,110,181,187,196,201,202,262,263,541,547,556,562,622,623,650,2521,2526,2527,2536,2539,2541 etc. all reaches 100%, the preventive effect of compound 199 grade is 98%, and the preventive effect of compound 2630 grade is 80%;
When liquor strength is 25mg/L, the preventive effect of compound 1,5,7,16,19,22,82,110,181,187,196,201,202,262,263,541,547,556,562,622,623,2521,2526,2527,2539 etc. all reaches 100%, the preventive effect of compound 199,650,2536 etc. is 98%, and the preventive effect of compound 2541 grade is 90%;
When liquor strength is 12.5mg/L, the preventive effect of compound 1,7,16,22,187,202,541,556,562,622,2521,2527 etc. all reaches 100%, the preventive effect of compound 19,82,201,263,623 etc. is 98%, the preventive effect of compound 650 grade is 95%, the preventive effect of compound 2536 grade is 90%, and the preventive effect of compound 196,2539 etc. is 85%;
When liquor strength is 6.25mg/L, the preventive effect of compound 7,16,22,187,202,541,562 etc. is 100%, and the preventive effect of compound 622 grade is 98%, and the preventive effect of compound 19,556 etc. is 95%, and the preventive effect of compound 196 grade is 85%.
Live body preventive effect to corn rust:
When liquor strength is 400mg/L, the preventive effect of compound 1,6,7,16,19,21,82,83,110,181,185,186,196,199,201,262,541,545,546,547,556,559,561,622,623,2521,2526,2536,2539,2630 etc. is 100%, and the preventive effect of compound 5,650,2527,2541 etc. is more than 80%;
When liquor strength is 100mg/L, the preventive effect of compound 6,7,21,110,201,262,545,546,559,561,622 etc. is 100%, the preventive effect of compound 196,199,556 etc. is 95%, the preventive effect of compound 185,186,623,2526 etc. is 90%, and the preventive effect of compound 19,82,181,547 etc. is more than 80%;
When liquor strength is 25mg/L, the preventive effect of compound 7,262,561,622 etc. is 100%, and the preventive effect of compound 559 grade is 98%, and the preventive effect of compound 545,546 etc. is 95%, and the preventive effect of compound 199 grade is 90%, and the preventive effect of compound 201 grade is 80%;
When liquor strength is 6.25mg/L, the preventive effect of compound 561,622 etc. is 95%, and the preventive effect of compound 262 grade is 90%, and the activity of compound 559 grade is 80%;
When liquor strength is 1.56mg/L, the preventive effect of compound 262 grade is 90%.
Live body preventive effect to wheat powdery mildew:
When liquor strength is 400mg/L, the preventive effect of compound 1,5,6,7,16,19,21,22,82,83,110,181,185,186,187,196,199,201,202,262,263,541,545,546,547,556,559,561,562,622,623,650,2536,2541 etc. is 100%, and the preventive effect of compound 2539 grade is 80%;
When liquor strength is 100mg/L, the preventive effect of compound 1 grade is 98%, and the preventive effect of compound 110,181 etc. is 90%, and the preventive effect of compound 5,7,22,82,541,545,562,2541 etc. is more than 80%.
(3) test result of part of compounds and contrast medicament
Carried out part of compounds and the active simultaneous test contrasting medicament, test result is shown " // " expression in 103(table in Table 100-and is not tested).Control compound is except KC1 to the KC19(known compound described in background parts) except, also synthesize following KC20 to KC23 in contrast with reference to prior art file:
The Antifungal Activity in Vitro of table 100 pair rice blast
The live body prolection of table 101 pair cucumber downy mildew
The live body prolection of table 102 pair corn rust
The live body prolection of table 103 pair wheat powdery mildew
Embodiment 9: pesticide and miticide actility measures
With the compounds of this invention, insecticidal activity assay test is carried out to several insect.Measuring method is as follows:
After testing compound dissolves with the mixed solvent of acetone/methanol (1:1), with containing 0.1%(wt) water of tween 80 is diluted to required concentration.
With small cabbage moth, black peach aphid, mythimna separata, carmine spider mite for target, airbrush spray method is adopted to carry out insecticidal activity assay.
(1) determination of activity of small cabbage moth, is killed
Measuring method: leaf dish cabbage leaves punch tool being broken into diameter 2cm, the pressure of airbrush spraying process is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf dish pros and cons spraying, spouting liquid is 0.5ml.Often process access after drying in the shade and try worm 10 2 ages, often process 3 times and repeat.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
As follows to the partial test result of small cabbage moth:
When liquor strength is 600mg/L, compounds 1,6,7,16,19,21,22,110,181,185,187,196,199,201,202,541,546,547,556,559,562,622,2527 etc. are 100% to small cabbage moth lethality rate, and compound 83,262,545,561,2526,2539 etc. are 86% to small cabbage moth lethality rate;
When liquor strength is 100mg/L, compound 196,546,547,556 etc. are 100% to small cabbage moth lethality rate, and compound 22 grade is 89% to small cabbage moth lethality rate, and compound 7,187,202 etc. are more than 80% to small cabbage moth lethality rate.
(2) determination of activity of black peach aphid, is killed
Measuring method: cut-off footpath 6cm culture dish, covers one deck filter paper at the bottom of ware, and drips appropriate tap water moisturizing.Clip suitable size (diameter is about 3cm) from the cabbage plant cultivating black peach aphid and the long cabbage leaves having 15 ~ 30 aphids, remove the aphid of alatae and face of blade, blade back is upwards placed in culture dish.The pressure of airbrush spraying process is 10psi (being roughly equal to 0.7kg/cm2), and spouting liquid is 0.5ml, often processes 3 times and repeats.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
As follows to the partial test result of black peach aphid:
When liquor strength is 600mg/L, compound 1,5,6,7,16,19,21,22,82,83,110,181,185,186,187,196,199,201,202,262,263,541,545,546,547,556,559,561,562,622,623,650,2527,2536,2539 etc. are 100% to the lethality rate of black peach aphid; Compound 2526 grade is 92% to the lethality rate of black peach aphid; Compound 2541 grade is 86% to the lethality rate of black peach aphid;
When liquor strength is 100mg/L, compounds 7,16,22,110,181,185,186,187,196,199,201,202,262,541,547,556,559,561,562,650 etc. are 100% to the lethality rate of black peach aphid, compounds 1,6 etc. are 99% to the lethality rate of black peach aphid, compound 545 grade is 96% to the lethality rate of black peach aphid, compound 21 grade is 90% to the lethality rate of black peach aphid, compound 546 grade is 88% to the lethality rate of black peach aphid, and compound 5 grade is 84% to the lethality rate of black peach aphid;
When liquor strength is 10mg/L, compound 22,181,187,202,547,562 etc. are 100% to the lethality rate of black peach aphid, and compound 7,186,196,541 etc. are more than 90% to the lethality rate of black peach aphid.
(3) determination of activity of mythimna separata, is killed
Measuring method: leaf section maize leaf being cut into long 2cm, the pressure of airbrush spraying process is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf section pros and cons spraying, spouting liquid is 0.5ml.Often process access after drying in the shade and try worm 10 2 ages, often process 3 times and repeat.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
As follows to the partial test result of mythimna separata:
When liquor strength is 600mg/L, compounds 1,6,7,16,19,21,22,181,187,196,199,201,202,541,546,547,556,559,561,562,2527 etc. are 100% to mythimna separata lethality rate, and compound 110,650,2541 etc. are 86% to the lethality rate of mythimna separata;
When liquor strength is 100mg/L, compound 22,187,199,202,547,559,561,562 etc. are 100% to mythimna separata lethality rate, and compound 196,201,650 etc. are 80% to the lethality rate of mythimna separata;
When liquor strength is 10mg/L, compound 187,547 etc. are 95% to mythimna separata lethality rate, and compound 562 grade is 83% to the lethality rate of mythimna separata.
(4) determination of activity of carmine spider mite, is killed
Measuring method: get two panels true leaf Kidney bean seedling, connects carmine spider mite and becomes mite and after investigating radix, carry out whole strain process with airbrush atomizer, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5ml.Often process and repeat for 3 times, process is placed on standard sight room, and 72 hours " Invest, Then Investigate " survival mite numbers, calculate mortality ratio.
As follows to the partial test result of carmine spider mite:
When liquor strength is 600mg/L, compounds 1,5,7,16,19,21,22,110,181,185,187,196,199,201,202,541,545,547,556,559,561,562,2539 etc. are 100% to carmine spider mite lethality rate, compound 546 grade is 90% to the lethality rate of carmine spider mite, and compound 83,623 etc. are 80% to the lethality rate of carmine spider mite;
When liquor strength is 100mg/L, compounds 7,16,22,181,187,199,202,547,556,559,562 etc. are 100% to the lethality rate of carmine spider mite, compounds 19,541 etc. are 96% to the lethality rate of carmine spider mite, compound 1 grade is 92% to the lethality rate of carmine spider mite, and compound 196,2539 etc. are more than 80% to the lethality rate of carmine spider mite;
When liquor strength is 10mg/L, compound 199,562 etc. are more than 85% to the lethality rate of carmine spider mite.
(5), the test result of part of compounds and contrast medicament
Carried out part of compounds and the active simultaneous test contrasting medicament, test result is shown " // " expression in 107(table in Table 104-and is not tested).Control compound ditto described in.
The preventive effect of table 104 pair small cabbage moth
The preventive effect of table 105 pair black peach aphid
The preventive effect of table 106 pair mythimna separata
The preventive effect of table 107 pair carmine spider mite
Claims (7)
1. replace fragrant oxy picolinate compounds, the compound of structure as shown in I-A
In formula:
R
1be selected from halogen, C
1-C
4alkyl or halo C
1-C
4alkyl;
R
2be selected from halogen;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen;
R
6, R
7, R
8be selected from hydrogen;
R
9be selected from hydrogen, halogen or C
1-C
4alkyl;
A is selected from NH;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
Or, the salt that general formula I-A compound and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
2. compound according to claim 1, is characterized in that: in general formula I-A
R
1be selected from chlorine, methyl, ethyl, CHF
2or trifluoromethyl;
R
2be selected from halogen;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen;
R
6, R
8be selected from hydrogen;
R
7be selected from hydrogen;
R
9be selected from hydrogen, halogen or C
1-C
4alkyl;
A is selected from NH;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
Or, the salt that general formula I-A compound and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
3. compound according to claim 2, is characterized in that: in general formula I-A
R
1be selected from chlorine, methyl, ethyl, CHF
2or trifluoromethyl;
R
2be selected from chlorine;
R
3be selected from hydrogen or methyl;
R
4, R
5be selected from hydrogen;
R
6, R
8be selected from hydrogen;
R
7be selected from hydrogen;
R
9be selected from hydrogen, chlorine or methyl;
A is selected from NH;
R
10, R
11, R
12, R
13may be the same or different, be selected from hydrogen, chlorine, methyl, trifluoromethyl, methoxyl group or trifluoromethoxy respectively;
Or, the salt that general formula I-A compound and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
4. compound according to claim 3, is characterized in that: in general formula I-A
R
1be selected from methyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13be selected from hydrogen, A is selected from NH; Or
R
1be selected from methyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
13be selected from hydrogen, R
12be selected from methyl, chlorine, methoxyl group or trifluoromethyl, A is selected from NH; Or
R
1be selected from ethyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
13be selected from hydrogen, R
12be selected from chlorine, trifluoromethyl or trifluoromethoxy, A is selected from NH; Or
R
1be selected from ethyl, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
11, R
13be selected from hydrogen, R
10, R
12be selected from chlorine, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13be selected from hydrogen, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
13be selected from hydrogen, R
12be selected from chlorine or trifluoromethyl, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
12, R
13be selected from hydrogen, R
11be selected from trifluoromethyl, A is selected from NH; Or
R
1be selected from CHF
2, R
2be selected from chlorine, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
11, R
13be selected from hydrogen, R
10, R
12be selected from chlorine, A is selected from NH;
Or, the salt that above-claimed cpd and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
5. a general formula I-A compound or its salt according to claim 1 prepares the purposes of sterilant, Insecticiding-miticiding agent medicine in agricultural, forestry or health field.
6. a sterilization and disinsection miticide composition, is characterized in that: containing, for example general formula I-A compound or its salt according to claim 1 as active ingredient, in composition, the weight percentage of active ingredient is 0.5-99%.
7. non-treatment object prevents and treats a method for germ in agriculture field, insect evil mite, it is characterized in that: imposed on by the composition according to claim 6 of significant quantity on described germ, insect evil mite or its growth medium.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412048.4A CN103772356B (en) | 2012-10-25 | 2012-10-25 | Replace fragrant oxy picolinate compounds and uses thereof |
| EP13849899.3A EP2913325B1 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| CN201380051597.6A CN104684900B (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| EP20184845.4A EP3760617B1 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| PCT/CN2013/085879 WO2014063642A1 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| US14/423,953 US9770026B2 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412048.4A CN103772356B (en) | 2012-10-25 | 2012-10-25 | Replace fragrant oxy picolinate compounds and uses thereof |
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| Publication Number | Publication Date |
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| CN103772356A CN103772356A (en) | 2014-05-07 |
| CN103772356B true CN103772356B (en) | 2016-03-23 |
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| CN201210412048.4A Active CN103772356B (en) | 2012-10-25 | 2012-10-25 | Replace fragrant oxy picolinate compounds and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105777717B (en) * | 2014-12-19 | 2019-07-26 | 沈阳中化农药化工研发有限公司 | Pyrazolyl pyrimidines ether compound and purposes |
| CN109776427B (en) * | 2017-11-13 | 2022-08-23 | 沈阳中化农药化工研发有限公司 | Pyrimidine diamine compound and application thereof |
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| AU7551894A (en) * | 1993-09-09 | 1995-03-27 | E.I. Du Pont De Nemours And Company | Fungicidal, miticidal and arthropodicidal aminopyrimidines |
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