CN105431433A - Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents - Google Patents
Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents Download PDFInfo
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- CN105431433A CN105431433A CN201480043333.0A CN201480043333A CN105431433A CN 105431433 A CN105431433 A CN 105431433A CN 201480043333 A CN201480043333 A CN 201480043333A CN 105431433 A CN105431433 A CN 105431433A
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- alkyl
- group
- cycloalkyl
- halogenated
- haloalkyl
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- 0 C*(*)C(*C(*)=CSC*=C)*(*)N Chemical compound C*(*)C(*C(*)=CSC*=C)*(*)N 0.000 description 12
- AYXZGIKVGOMFBS-UHFFFAOYSA-N CC(Cc1c(C(F)(F)F)ccc(-c([n]2C)nc3c2ncc(C(F)(F)F)c3)c11)S1(=O)=O Chemical compound CC(Cc1c(C(F)(F)F)ccc(-c([n]2C)nc3c2ncc(C(F)(F)F)c3)c11)S1(=O)=O AYXZGIKVGOMFBS-UHFFFAOYSA-N 0.000 description 1
- WFHFHVXZOYHCPK-UHFFFAOYSA-O CC(c1ncc(C(F)(F)F)cc1[SH+](C)=O)=O Chemical compound CC(c1ncc(C(F)(F)F)cc1[SH+](C)=O)=O WFHFHVXZOYHCPK-UHFFFAOYSA-O 0.000 description 1
- WPVDXQQQXNAEKR-UHFFFAOYSA-N CC1(N=C(C(F)(F)F)SC1c1nc2cc(C(F)(F)F)ncc2[n]1C)Br Chemical compound CC1(N=C(C(F)(F)F)SC1c1nc2cc(C(F)(F)F)ncc2[n]1C)Br WPVDXQQQXNAEKR-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N CCCCN(C)C Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- MAKZMFMTYSASHE-UHFFFAOYSA-N CCOC(c1c(SCC)[s]cn1)=O Chemical compound CCOC(c1c(SCC)[s]cn1)=O MAKZMFMTYSASHE-UHFFFAOYSA-N 0.000 description 1
- MDUYVPDMJAAFFO-UHFFFAOYSA-N CCS(c1cc(C(F)(F)F)cnc1-c1n[n](cnc(C(F)(F)F)c2)c2n1)(=O)=O Chemical compound CCS(c1cc(C(F)(F)F)cnc1-c1n[n](cnc(C(F)(F)F)c2)c2n1)(=O)=O MDUYVPDMJAAFFO-UHFFFAOYSA-N 0.000 description 1
- FPVPOHJHMQZOCR-UHFFFAOYSA-N CCSc1cc(C(F)(F)F)cnc1-c1nc2cc(C)nnc2[n]1C Chemical compound CCSc1cc(C(F)(F)F)cnc1-c1nc2cc(C)nnc2[n]1C FPVPOHJHMQZOCR-UHFFFAOYSA-N 0.000 description 1
- RNORWDFXIJJNMO-UHFFFAOYSA-N CCSc1n[s]nc1-c1nc2cc(C(F)(F)F)cnc2[n]1C Chemical compound CCSc1n[s]nc1-c1nc2cc(C(F)(F)F)cnc2[n]1C RNORWDFXIJJNMO-UHFFFAOYSA-N 0.000 description 1
- QXOIJMWKWJXYSS-UHFFFAOYSA-N Cc1c(C(N(C)OC)=O)[s]c(C(F)(F)F)n1 Chemical compound Cc1c(C(N(C)OC)=O)[s]c(C(F)(F)F)n1 QXOIJMWKWJXYSS-UHFFFAOYSA-N 0.000 description 1
- QFJXTWRTRFSCIX-UHFFFAOYSA-N [O-][N+](c1cc(C(F)(F)F)ncc1O)=O Chemical compound [O-][N+](c1cc(C(F)(F)F)ncc1O)=O QFJXTWRTRFSCIX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
Abstract
Pesticidally active bi-or tricyclic heterocycles with sulphur-containing substituents, stereoisomers and tautomeric forms thereof that can be used as insecticides and can be prepared in a manner known per se.
Description
The present invention relates to there is insecticidal activity sulfur heterocyclic ring derivative, relate to for the preparation of they method, relate to the composition that comprises these compounds and relate to their purposes for controlling animal pest biology (comprising arthropods and the representative of especially insect or acarina).
To have the heterogeneous ring compound killing harmful organism effect be known and describe in such as WO2009/131237, WO2011/043404, WO2011/040629, WO2010/125985, WO2012/086848, WO2013/018928, WO2013/191113, WO2013/180193 and WO2013/180194.
Have been found that now the multiple new Hete rocyclic derivatives having and kill harmful organism characteristic.
Therefore the present invention relates to the compound with Formula I,
A-B(I)，
Wherein A is a group being selected from lower group, and this group is by chemical formula A
1to A
8composition:
Wherein arrow represents the point being attached to group B; And
B is a group being selected from lower group, and this group is by chemical formula B
1to B
11composition:
Wherein arrow represents the point being attached to group A;
Wherein
L
1methylene radical or a direct key;
V
0nitrogen or CR
5;
V
1nitrogen or CR
20; V
2nitrogen or CR
21; V
3nitrogen or CR
22; V
4nitrogen or CR
23;
V
5nitrogen or CR
24; V
6nitrogen or CR
25; V
7nitrogen or CR
26; V
8nitrogen or CR
27;
V
9nitrogen, or CR
28; V
10nitrogen or CR
29; V
11nitrogen or CR
30;
G
1nitrogen or CR
31;
G
2nitrogen or CR
32;
G
3-NR
35, Sauerstoffatom or a sulphur atom;
G
4nitrogen or CR
33;
G
5nitrogen or CR
34;
J
1, J
2, J
3form 5 yuan of heterocycles together, this heterocycle can be saturated or unsaturated, and comprise one or two atom being selected from lower group, this group is made up of nitrogen, oxygen and sulphur, and it is monosubstituted or polysubstituted that this ring can be selected from the substituting group of lower group, and this group is by C
1-C
6alkyl, halogen and or C
1-C
6haloalkyl forms, and its condition is if this ring comprises two Sauerstoffatoms or two sulphur atoms, and they by a carbon atom separately;
R
1and R
2identical or different and each expression hydrogen, halogen, C
1-C
6alkyl or C
1-C
6haloalkyl;
R
3be one and can be selected from the monosubstituted or polysubstituted C of the substituting group of lower group
1-C
6alkyl, C
2-C
6thiazolinyl or C
2-C
6alkynyl group, this group is by C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen, C
3-C
6cycloalkyl forms, described C
3-C
6cycloalkyl itself can be selected from halogen and C
1-C
3the substituting group of alkyl is monosubstituted or polysubstituted; And monosubstituted or polysubstituted by 5-or 6-unit heterocyclic group, it is monosubstituted or polysubstituted that this heterocyclic group can be selected from the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
Or R
3-CO
2r
36,-C (O) R
36or hydrogen;
Or R
3to be selected from the monosubstituted or polysubstituted C of the substituting group of lower group
3-C
6cycloalkyl, this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group and halogen composition;
Or R
3be one and can be selected from monosubstituted or polysubstituted 5-or the 6-unit heterocyclic group of the substituting group of lower group, this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
R
35be hydrogen, the monosubstituted or polysubstituted C of the substituting group of lower group can be selected from
1-C
6alkyl, this group is by C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl forms, described C
3-C
6cycloalkyl itself can be selected from halogen and C
1-C
3the substituting group of alkyl is monosubstituted or polysubstituted; Or its a kind of N-oxide compound;
R
4, R
5, R
20, R
21, R
22, R
23, R
24, R
25, R
26, R
27, R
28, R
29and R
30be identical or different, and represent cyano group, nitro, halogen, hydroxyl, C
1-C
6alkene oxygen base, C
1-C
6-halogenated alkoxy ,-C (O) R
36-C (O) R
36or hydrogen; Or
Monosubstituted or the polysubstituted C of the substituting group of lower group can be selected from
1-C
6alkyl, this group is by cyano group, halogen, hydroxyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl forms, and described cycloalkyl itself can be selected from the substituting group replacement of lower group, and this group is by halogen and C
l-C
3alkyl forms; Or represent
One can be selected from the monosubstituted or polysubstituted phenyl group of the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18and R
19be identical or different, and represent C
1-C
6alkyl, C
1-C
6haloalkyl or hydrogen, and group CR in addition
13r
14can be a carbonyl group C=O;
R
31, R
32, R
33, R
34and R
40be identical or different, and represent C
1-C
6alkyl, C
1-C
6haloalkyl ,-OR
7,-S (O)
nr
36,-NR
36r
37,-CO
2r
36,-C (O) R
36, cyano group, nitro, halogen or hydrogen;
R
36and R
37be identical or different, and represent hydrogen, the monosubstituted or polysubstituted C of following substituting group can be selected from
1-C
6alkyl: C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl, wherein said C
3-C
6it is monosubstituted or polysubstituted that cycloalkyl can be selected from the substituting group of lower group, and this group is by halogen and C
l-C
3alkyl forms; Or
R
36and R
37be identical or different, and represent
One can be selected from the monosubstituted or polysubstituted phenyl group of the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
Each m represents 0,1 or 2 independently, and n represents 0,1 or 2, and its condition is:
A) at-S (O)
nr
36in, when n is 0, R
36hydrogen;
If b) B is B
1, so A is and A
2, A
3and A
5different;
If c) A is A
1, so B is and B
1, B
7, B
8, B
9and B
10different;
If d) A is A
5, so B is and B
10different;
Together with salt acceptable in agrochemicals, enantiomer, diastereomer, tautomer, and the N-oxide compound of these compounds.
The compound with Formula I with at least one basic center can form such as acid salt with following acid, these acid are: such as strong inorganic acid (such as mineral acid, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or haloid acid), strong organic carboxyl acid (that be such as unsubstituted or that picture is optionally substituted by halogen C
1-C
4alkane carboxylic acid, such as acetic acid (as saturated or undersaturated dicarboxylic acid), such as oxalic acid, propanedioic acid, succsinic acid, toxilic acid, fumaric acid or phthalic acid (as hydroxycarboxylic acid), such as xitix, lactic acid, oxysuccinic acid, tartrate or citric acid, or picture phenylformic acid), or organic sulfonic acid (that be such as unsubstituted or that picture is optionally substituted by halogen C
1-C
4alkane-or aryl sulfonic acid, such as methane-or tosic acid).The compound with Formula I with at least one acidic-group can be such as, (such as mineral salt is (as basic metal or alkaline earth salt to form salt with alkali, such as sodium salt, sylvite or magnesium salts)), with ammonia or organic amine (as morpholine, piperidines, tetramethyleneimine, list-, two-or three-Iower-alky amine (such as ethyl-, diethyl-, triethyl-or dimethyl propylamine), or single-, two-or trihydroxy--Iower-alky amine (such as single-, two-or trolamine)) form salt.
The alkyl occurred in substituting group definition can be straight chain or side chain, and is such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, nonyl, decyl and their branched chain isomer.Alkoxyl group, thiazolinyl and alkynyl group are derived from mentioned alkyl group.Thiazolinyl and alkynyl group can be single or polyunsaturated.
Halogen is generally fluorine, chlorine, bromine or iodine.Correspondingly, this is also applicable to the halogen be combined with other implications, such as haloalkyl or halogenophenyl.
Halogenated alkyl group preferably has a chain length from 1 to 6 carbon atom.Haloalkyl is such as methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyls, 2-fluoro ethyl, 2-chloroethyl, pentafluoroethyl group, 1,1-bis-fluoro-2,2,2-trichloroethyl, 2,2,3,3-tetra-fluoro ethyl and 2,2,2-trichloroethyl; Preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
Alkoxy base preferably has one preferably from the chain length of 1 to 6 carbon atom.Alkoxyl group is, such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert.-butoxy and be isomeric pentyloxy and hexyloxy group; Preferably methoxyl group and oxyethyl group.
Alkoxy carbonyl is, such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl or ethoxy carbonyl.Halo alkoxy group preferably has a chain length from 1 to 6 carbon atom.Halogenated alkoxy is, such as fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, 2,2,2-trifluoro ethoxy, 1,1,2,2-tetrafluoro oxyethyl group, 2-fluorine oxyethyl group, 2-chloroethoxy, 2,2-difluoroethoxies and 2,2,2-tri-chloroethoxy base, preferably difluoro-methoxy, 2-chloroethoxy and trifluoromethoxy.
Alkylthio radicals preferably has a chain length from 1 to 6 carbon atom.Alkylthio is, such as methylthio group, ethylmercapto group, rosickyite base, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio or tertiary butylthio, preferably methylthio group and ethylmercapto group.Alkyl sulphinyl is, such as methylsulfinyl, ethylsulfinyl, propylsulfenyl base, isopropylsulphinyl, n-butylsulfinyl, isobutyl-sulfinyl, sec-butyl sulfinyl, terf-butylsulfinyl; Preferably methylsulfinyl and ethylsulfinyl.
Alkyl sulphonyl is, such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base base, isopropelsulfonyl, normal-butyl alkylsulfonyl, iso-butylsulfonyl, sec-butylsulfonyl or tert. butylsulfonyl; Preferably methyl sulphonyl or ethylsulfonyl.
Alkylamino is, such as methylamino-, ethylamino, n-propylamine base, isopropylamino or isomeric butylamine.Dialkylamino is, such as dimethylamino, methylethylamine, diethylin, n-propyl-methylamino, dibutylamino and diisopropylaminoethyl.Preferably there is the alkylamino group from 1 to 4 carbon atom chain length.
Alkoxyalkyl preferably has the chain length of 1 to 6 carbon atom.
Alkoxyalkyl is, such as methoxymethyl, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, n-propoxymethyl, positive propoxy ethyl, i-propoxymethyl or isopropoxyethyl.
These groups of naphthene base preferably have from 3 to 6 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.Phenyl, also as the part of a substituting group (such as phenoxy group, benzyl, benzyloxy, benzoyl, thiophenyl, phenylalkyl, phenoxyalkyl), can be substituted.In this case, these substituting groups can be in ortho position, a position and/or contraposition.Preferred the position of substitution is ortho position and the para postion of this ring attach site.
In the context of the present invention, " single to polysubstituted " in substituting group definition typically refers to, depends on substituent chemical structure, mono-substituted to replace for seven times, preferably mono-substituted to five replacements, is more preferably list, two or trisubstituted.
" 5-unit heterocycle " in the present invention refers to a 5-membered aromatic heterocycle group or 5-unit Non-aromatic heterocyclic groups, and " 6-unit heterocycle " refers to a 6-membered aromatic heterocycle group or 6-unit Non-aromatic heterocyclic groups.Therefore, " 5-or 6-unit heterocyclic group " in the present invention refers to a 5-or 6-membered aromatic heterocycle group, or a 5-or 6-unit Non-aromatic heterocyclic groups.
" 5-or the 6-unit heterocyclic group that can be substituted " in the present invention refers to a heterocyclic group, the one or more hydrogen atoms be wherein attached on one or more carbon atom, one or more nitrogen-atoms and/or one or more sulphur atom are optionally selected from one or more atom or the group replacement of a predefine inventory, wherein this group has two or more atoms or group of being selected from a predefine inventory, and these atoms or group are same to each other or different to each other.In the background of atom N or S atom, when it is oxidized with a kind of N oxide compound of each self-forming or sulfone and sulfoxide, this oxidized analogue is unsubstituted; But so a kind of analogue within the scope of the present invention.
The example of 5-or the 6-unit heterocyclic group that can be substituted comprises tetramethyleneimine-l-base group, 3,3,4,4-tetra-fluoropyrrolidine-l-base groups, tetrahydrofuran (THF)-2-base group, piperidinyl group, morpholinyl group, thiomorpholinyl groups etc.
The example of 5-or the 6-membered aromatic heterocycle group that can be substituted is 2-pyrryl, 2-furanyl group, 3-furyl, 5-pyrazolyl, 4-pyrazolyl, 1-pyrryl, l-methyl-2-pyrryl, 2-methylsulfanyl-l-pyrryl, 2-methylsulfinyl-1-pyrryl, 2-methyl sulphonyl-l-pyrryl, 2-methylamino-l-pyrrolyl group, 2-dimethylamino-l-pyrrolyl group, the bromo-2-furyl of 5-, 5-nitro-2-furyl group, 5-cyano group-2-furanyl group, 5-methoxyl group-2-furanyl group, 5-ethanoyl-2-furyl, 5-methoxycarbonyl-2-furanyl group, 2-methyl-3-furyl group, 2,5-dimethyl-3-furanyl group, 2,4-dimethyl-3-furanyl group, 5-methyl-2-thienyl group, 3-methyl-2-thienyl group, l-methyl-3-trifluoromethyl-5-pyrazolyl groups, chloro-l, the 3-dimethyl of 5--4-pyrazolyl groups, pyrazoles-l-base group, the chloro-pyrazoles of 3--l-base group, 3-bromo pyrazoles-l-base group, 4-chloropyrazole-l-base group, 4-bromo pyrazoles-l-base group, imidazoles-l-base group, 1,2,4-triazole-l-base group, the chloro-l of 3-, 2,4-triazole-l-base group, pyrrotriazole-l-base group, 1,2,3,5-tetrazolium-l-base group, 2-thienyl group, 3-thienyl group, 3-Trifluoromethyl-1,2,4-triazole-l-base group, 4-trifluoromethyl pyrazol-l-base group, pyrazinyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-Pyridyl residues, 3-Pyridyl residues, 4-Pyridyl residues, the fluoro-2-Pyridyl residues of 3-, the fluoro-2-Pyridyl residues of 4-, the fluoro-2-Pyridyl residues of 5-, the fluoro-2-Pyridyl residues of 6-, 2-pyrimidyl group, 3-chloro-5-trifluoromethylpyridine-2-base group, 5-5-flumethiazine-2-base group etc.
In a preferred embodiment of the invention, R
35to be selected from the monosubstituted or polysubstituted C of the substituting group of lower group
1-C
6alkyl, this group is by C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl forms, described C
3-C
6cycloalkyl itself can be selected from halogen and C
1-C
3the substituting group of alkyl is monosubstituted or polysubstituted; Or its a kind of N-oxide compound.
Preferably R
4, R
5, R
20, R
21, R
22, R
23, R
24, R
25, R
26, R
27, R
28, R
29, and R
30be identical or different, and represent cyano group, nitro, halogen, hydroxyl ,-C (O) R
36or hydrogen; Or
Monosubstituted or the polysubstituted C of the substituting group of lower group can be selected from
1-C
6alkyl, this group is by cyano group, halogen, hydroxyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl forms, and described cycloalkyl itself can be selected from the substituting group replacement of lower group, and this group is by halogen and C
l-C
3alkyl forms; Or represent
One can be selected from the monosubstituted or polysubstituted phenyl group of the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form.
The compound with chemical formula (I) is made up of the combination of the group being selected from group A with the group being selected from group B.
Therefore, in one embodiment of the invention, this compound with chemical formula (I) is one and is selected from the group of A and is selected from any one group of group B, such as
A) group A
1with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition;
B) group A
2with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition;
C) group A
3with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition;
D) group A
4with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition;
E) group A
5with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition;
F) group A
6with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition;
G) group A
7with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition; Or
H) group A
8with the moiety combinations being selected from lower group, this group is by group B
1to B
11composition.
Similarly, in another embodiment, this compound with chemical formula (I) is one and is selected from the group of B and is selected from any one group of group A, such as
A) group B
1with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
B) group B
2with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
C) group B
3with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
D) group B
4with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
E) group B
5with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
F) group B
6with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
H) group B
7with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
E) group B
8with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
F) group B
9with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition;
G) group B
10with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition; Or
H) group B
11with the moiety combinations being selected from lower group, this group is by group A
1to A
8composition.
In an other embodiment, group A is from A
1to A
8be selected from the following Q of group more specifically
1to Q
11in any one, wherein R
1as defined in a first aspect:
The other embodiment of this first aspect is listed in following table Z:
Table Z: for the combination of chemical formula (I) A and B
In one embodiment of the invention, a preferred group A is A
1, A
6, or A
4; Especially preferably A
1and A
6; Particularly A
1.
In another preferred embodiment of the invention, a preferred group B is B
1, B
2, B
11, B
7, B
8, B
9, B
10, B
3or B
6; Especially preferably B
1, B
2, B
11, B
7, B
8, B
9, or B
10, particularly B
1, B
2, B
11, B
7, B
8or B
9; Such as B
1, B
2or B
11.
Therefore, chemical formula (I) is preferably made up of the following combination of group A and B:
In one embodiment of the invention, if B
1in V
0cR
5, A is and A
1different.In a preferred embodiment, B
1in V
0cR
5, and A is selected from A
2, A
3, A
4, A
5and A
6, be especially selected from A
4and A
6.
In one embodiment of the invention, about each B, L
1it is a direct key.
In another embodiment of the present invention, about each A, R
1identical or different and each expression hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably hydrogen, bromine, chlorine, methyl, difluoromethyl or trifluoromethyl.
In another embodiment of the present invention, about each A, R
2identical or different and each expression hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably hydrogen.
In another embodiment of the present invention, about each B, R
3identical or different and each expression C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably methyl or ethyl.
In another embodiment of the present invention, about each B, R
4identical or different and each expression hydrogen or C
1-C
3alkyl; Preferably hydrogen or methyl.
The compound with Formula I further preferably represented by a combination of above-mentioned 4 " another embodiment " groups.
In another embodiment of the present invention, be identical or different and each expression 0,1 or 2 about each B, m; Be preferably 2.
In another embodiment of the present invention, about each B, R
6and R
7identical or different and each expression C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably methyl.
In another embodiment of the present invention, about each B, R
10and R
11identical or different and each expression hydrogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably hydrogen or methyl.In a preferred embodiment, R
11be hydrogen and R
10it is methyl.
In another embodiment of the present invention, about each B, R
12, R
13, and R
14identical or different and each expression hydrogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably hydrogen or methyl.In a preferred embodiment, R
13and R
14each hydrogen naturally and R
12it is methyl.
In another embodiment of the present invention, about each B, R
15, R
16, R
17and R
18identical or different and each expression hydrogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably hydrogen or methyl.In a preferred embodiment, R
15, R
16, R
17and R
18each hydrogen naturally.
In another embodiment of the present invention, about each B, R
19be identical or different and represent hydrogen, C
1-C
4alkyl or C
1-C
4haloalkyl; Preferably hydrogen or the tertiary butyl.
In another embodiment of the present invention, about each B, V
1be identical or different and represent CH or N.
In another embodiment of the present invention, about each B, V
0be identical or different and represent CH or N.
In another embodiment of the present invention, about each B, V
2be identical or different and represent R
21 ', wherein R
21 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl, C
1-C
3haloalkyl or phenyl or 4-trifluoromethyl, preferably hydrogen, chlorine, bromine or trifluoromethyl.
In another embodiment of the present invention, about each B, V
3be identical or different and represent CR
22 ', wherein R
22 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl, preferably hydrogen, chlorine, bromine or trifluoromethyl.
In another embodiment of the present invention, about each B, V
4be identical or different and represent N or CR
23 ', wherein R
23 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
4represent N or CH.
In another embodiment of the present invention, about each B, V
5be identical or different and represent N or CR
24 ', wherein R
24 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
5represent CH.
In another embodiment of the present invention, about each B, V
6be identical or different and represent N or CR
25 ', wherein R
25 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
6represent N or CH.
In another embodiment of the present invention, about each B, V
7be identical or different and represent N or CR
26 ', wherein R
26 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
7represent N, CH, C-chlorine, C-bromine or C-CF
3.
In another embodiment of the present invention, about each B, V
8be identical or different and represent N or CR
27 ', wherein R
27 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
8represent CH.
In another embodiment of the present invention, about each B, V
9be identical or different and represent N or CR
28 ', wherein R
28 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
9represent N or CH.
In another embodiment of the present invention, about each B, V
10be identical or different and represent N or CR
29 ', wherein R
29 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
9represent N or CH.
In another embodiment of the present invention, about each B, V
11be identical or different and represent N or CR
30 ', wherein R
30 'about each B, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably V
9represent N or CH.
In another embodiment of the present invention, about each A, G
1be identical or different and represent N or CR
31 ', wherein R
31 'about each A, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably G
1represent N or CH.
In another embodiment of the present invention, about each A, G
2be identical or different and represent N or CR
32 ', wherein R
32 'about each A, be identical or different and represent hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably G
2represent N or CH.
In another embodiment of the present invention, about each A, G
3be identical or different and represent oxygen, sulphur or NR
35 ', wherein R
35be N-methyl, about each A, be identical or different and represent C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably G
3represent oxygen, sulphur or N-CH
3.
In another embodiment of the present invention, about each A, G
4be identical or different and represent N or CR
33 ', wherein R
33 'about each A, be identical or different and represent C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably G
4represent N or N-CH
3.
In another embodiment of the present invention, about each A, G
5be identical or different and represent N or CR
34 ', wherein R
34 'about each A, be identical or different and represent hydrogen, C
1-C
3alkyl or C
1-C
3haloalkyl; Preferably G
5represent N or N-CH
3.
In another embodiment of the present invention, about each group A
4, J
1n.
In another embodiment of the present invention, about each group A
4, J
2cH, C
1-C
3alkyl or C
1-C
3haloalkyl, such as CH, C-CH
3, or C-CF
3.
In another embodiment of the present invention, about each group A
4, J
3oxygen or sulphur.
For the preparation of have chemical formula (I) compound be undertaken by known to persons of ordinary skill in the art or such as described in WO2009/131237, WO2011/043404, WO2011/040629, WO2010/125985, WO2012/086848, WO2013/018928, WO2013/191113, WO2013/180193 and WO2013/180194 method substantially according to method of the present invention, and relate to the compound with Formulae II
(wherein Q is group B
1, B
2, B
3, B
4, B
5, B
6, B
7, B
8, B
9and B
11, wherein R
3, R
4, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19, V
0, V
1, V
2, V
3, V
4, V
5, V
6, V
7, V
8and L
1as described in Formula I, and group B
1-B
9and B
11in arrow show the point be attached on the carbonyl atom of carboxylic group in Formulae II) with there is the compound of Formulae II, IV or V;
(wherein R
1, R
2, G
1, G
2, and G
5be as described in chemical formula (I) and M
1oxygen, sulphur or NR
35), the reaction occurred under 150 DEG C to the temperature of 200 DEG C under the existence of a kind of dewatering agent such as Tripyrophosphoric acid, to produce the compound with Formula I a, Ib and Ic, wherein these substituting groups are as described in for chemical formula (I).
Such process is well-known, and at such as WO2011/040629 or WO2009131237 (M
1oxygen), WO2011088990 or Chinese Journal of Inorganic Chemistry (Inorg.ChimicaActa), 358 (9), 2701-2710; 2005 (M
1sulphur) and JACS (J.Am.Chem.Soc.), 132 (5), 1545-1557,2010 or WO2008128968 (M
1nR
35) middle description.In scheme 1, outline the method for the compound with Formula I a:
scheme 1
As seen in scheme 1, the formation of Ia is the intermediary of the compound by having chemical formula VI and occurs.In many cases, it is favourable for so preparing the compound with chemical formula (I) by this kind of intermediate.In scheme 2, this point is described for the compound with Formula I a.
scheme 2.
In scheme 2, by known to persons of ordinary skill in the art and be described in such as tetrahedron (Tetrahedron), 61 (46), 10827-10852, method in 2005, activates the compound for having Formulae II a by the compound (wherein Q is foregoing) with Formulae II.Such as wherein X
0be the compound of halogen be by under the existence of the DMF of catalytic amount, in inert solvent such as methylene dichloride or THF, at the temperature (preferably 25 DEG C) between 20 DEG C to 100 DEG C, carry out process formation with such as oxalyl chloride or thionyl chloride.Optionally under the existence of a kind of alkali (such as triethylamine or pyridine), form the compound with chemical formula VI with the compound treatment IIa with Formulae II I.Alternately, can by a kind of inert solvent (such as pyridine or THF), optionally under the existence of a kind of alkali (such as triethylamine), at temperature between 50 DEG C-180 DEG C, there is the compound of Formulae II, to provide kind IIa (the wherein X be activated with dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) process
0x respectively
01and X
02) prepare the compound with chemical formula VI.Then, the compound with chemical formula VI of such acquisition is by under the existence of a kind of acid catalyst (such as methylsulfonic acid or tosic acid), in a kind of inert solvent (such as the pyridine of N-methylpyrrole), between 25 DEG C-180 DEG C (preferably 130 DEG C-170 DEG C) temperature under, carry out dewatering (such as by heating this compound in microwave) is converted into the compound with Formula I a.Previously in WO2010125985, described these class methods.Alternately, in a kind of inert solvent (such as THF), at temperature between 25 DEG C-50 DEG C, triphenylphosphine, di-isopropyl azodicarboxy hydrochlorate can be used to be compound (the wherein M with Formula I a by the converting compounds with chemical formula VI
1o).Previously describing this kind of light for this kind of conversion prolonged reaction (Mitsunobu) condition (see WO2009131237).The application of these class methods that the compound with Formulae II and IIa reacts with the compound with Formula I V and V respectively produces compounds ib and Ic via intermediate VII and VIII respectively.
Alternately, there is the compound of chemical formula (I) by making to have the compound of Formula I X, X, XI, XII and XIII;
(wherein V
0, V
1, V
2, V
3, V
4, V
5, V
6, V
7, V
8and R
4as defined for chemical formula (I), and X
04halogen) with as described in scheme 2 and 3 there is Formulae II I, the compound of IV and V reacts, prepare to provide the compound with following chemical formula: XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XIV, XV, XVI, XVII and XVIII;
(wherein R
1, R
2, R
4, G
1, G
2, G
5, V
0, V
1, V
2, V
3, V
4, V
5, V
6, V
7, V
8, J
1, J
2and J
3as defined in Formula I, M
1oxygen, sulphur or NR
35, and X
04halogen).The compound with chemical formula XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII can with the compound with chemical formula XXIX
R
3-SH(XXIX)
(wherein R
3as described in Formula I), under the existence of a kind of suitable alkali (such as basic metal carbonate (such as sodium carbonate and salt of wormwood) or basic metal hydride (such as sodium hydride)), in a kind of applicable solvent, react at temperature between 25 DEG C-120 DEG C, to provide the compound with Formula I d, Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip, Iq and Ir:
Needing the example of the solvent used in the reaction comprises ether, such as THF, glycol dimethyl ether, t-butyl methyl ether and Isosorbide-5-Nitrae-diox, and aromatic hydrocarbon such as toluene and dimethylbenzene, nitrile is acetonitrile such as.(as such as in WO2013018928) similar chemical process had previously been described.Alternately, this reaction can under the existence of a kind of palladium catalyst (such as three (dibenzalacetone) two palladium (0)), at a kind of phosphorus part (such as 4, the two diphenylphosphine-9 of 5-, 9-dimethyl xanthene (xanthphos)) existence under, in a kind of inert solvent (such as dimethylbenzene), carry out at temperature (preferably 140 DEG C) between 100 DEG C-160 DEG C, as by Perry about the people such as (Perrio) at tetrahedron (Tetrahedron), 61,5253-5259, described in 2005.The compound (wherein m is 1 or 2) represented by chemical formula (I) has Formula I d by oxidation, the compound of Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip, Iq and Ir produces.This oxidizing reaction is normally carried out under a kind of existence of solvent.Need the example of the solvent used in the reaction comprise aliphatic halogenated hydrocarbon (such as methylene dichloride and chloroform), alcohol (such as methyl alcohol and ethanol), acetic acid, water, and composition thereof.Needing the example of the oxygenant used in the reaction comprises sodium periodate and metachloroperbenzoic acid.Need the amount of the oxygenant used in the reaction normally relative to 1 mole compound Id, Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip, 1 to 3 mole of Iq and Ir, preferably 1 to 1.2 mole, to produce compound (I) (wherein the m=1) with chemical formula, and preferably relative to 1 mole compound Id, Ie, If, Ig, Ih, Ii, Ij, Ik, Il, Im, In, Io, Ip, the oxygenant (preferred metachloroperbenzoic acid) of 2 to 2.2 moles of Iq and Ir, to produce the compound (wherein m=2) with chemical formula (I).
(wherein B is B to have the compound of Formula I
10) by making the compound with chemical formula XXX:
Q
1-X
05(XXX)，
(wherein Q
1a
1, A
2, A
3, A
4, and A
8, and X
05a kind of halogen or a leavings group OSO
2r
38, and at A
1, A
2, A
3, A
4, and A
6in these substituting groups in arrow display group A attach to substituent X
04on point, and wherein R
38optionally by nitro or C
1-C
3the C that alkyl replaces
1-C
6alkyl, C
1-C
6haloalkyl or phenyl) with there is the compound of chemical formula XXXI;
(wherein V
9, V
10, and V
11as described in Formula I), under the existence of a kind of applicable alkali (such as sodium hydride or cesium carbonate), in a kind of inert solvent (such as dimethyl formamide, the pyridine of N-methylpyrrole or acetonitrile), carry out reacting to produce the compound with chemical formula XXXII at the temperature between 20 DEG C-150 DEG C and prepare:
Alternately, the compound with chemical formula XXXII can by making to have the compound of chemical formula XXX and having the compound of chemical formula XXXI in a kind of inert solvent (such as diox), at the cuprous iodide of catalytic amount and a kind of diamines (such as N of catalytic amount, N-dimethyl-ethylenediamine or the trans-N of racemize, N-dimethyl cyclohexane diamines) existence under, and a kind of alkali (such as salt of wormwood or the potassiumphosphate) temperature between 50 DEG C-120 DEG C (preferably 90 DEG C-110 DEG C) reacting obtains.This kind of reaction has good precedent in the literature, and at such as organic chemistry magazine (J.Org.Chem.), 68,2609-2617, and 2003 and organic bulletin (Org.Letts.), 9,643-646, describes in 2007.Have chemical formula XXXII compound can with a kind of halide reagent (such as phosphoryl chloride, phosphorus trichloride or phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide or thionyl chloride), optionally in a kind of inert solvent, react at temperature between 25 DEG C-120 DEG C, to provide compound (the wherein X with chemical formula XXXIII
06halogen):
Subsequently, the compound with chemical formula XXXIII can with the compound with chemical formula XXIX;
R
3-SH(XXIX)
(wherein R
3as described in Formula I), at a kind of applicable alkali (such as alkaline earth metal hydride, such as sodium hydride) and a kind of polar aprotic solvent (such as dimethyl formamide) existence under, process at temperature between 25 DEG C-120 DEG C, to provide the compound with Formula I s:
The oxidation of compound is undertaken by method known to persons of ordinary skill in the art, sodium periodate is such as used to have the compound (wherein m=1) of Formula I t with preparation, or at least two metachloroperbenzoic acids (MCPBA) of equivalent, in a kind of inert solvent (such as methylene dichloride), produce the compound (wherein m=2) with Formula I t.
This synthesis is outlined in scheme 3.
scheme 3
(wherein A is A to have the compound of Formula I
2and G
5cR
34) subgroup can be represented by the compound with Formula I u
Wherein Q is group B
1, B
2, B
3, B
4, B
5, B
6, B
7, B
8, B
9or B
11in one, and R
1, R
2, G
1, G
2and G
4as described in chemical formula (I), and R
34c
1-C
6alkyl or C
1-C
6haloalkyl, by making the compound with chemical formula XXXIV
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I)) and a kind of compound with chemical formula XXXV
(wherein X
07a kind of halogen or a leavings group OSO
2r
38, and Q is as defined above), optionally under a kind of existence of applicable alkali, react in a kind of inert solvent and prepare.
A kind of other method that preparation has a compound of Formula I u relates to makes to have the compound of chemical formula XXXIV and the compound of XXXVa
Under the existence of a kind of Lewis acid (such as zinc iodide (II) or trifluoromethayl sulfonic acid indium (III)), at a kind of inert solvent (such as chlorobenzene or 1,2, dichlorobenzene) in, with a kind of copper (II) salt (such as acetic acid Cu (II)) of catalysis, under oxygen or air atmosphere, react at temperature (preferably 110 DEG C-140 DEG C) between 100 DEG C-180 DEG C, to provide compound (the wherein R with Formula I u
34hydrogen).Previously at document (see senior synthesis and catalysis (Adv.Synth.Catal.) 2013,355,1741-1747, and organic chemistry magazine (J.Org.Chem.), 2013,78,12494-12504) in describe this kind of reaction.In a kind of polar aprotic solvent (such as acetonitrile or dimethyl formamide), at ambient temperature, there is with a kind of halogenating agent (such as N-chloro succinic diamide, N-bromosuccinamide or N-iodosuccinamide) halogenation compound (the wherein R of Formula I u
34hydrogen) produce there is Formula I u
ccompound
Wherein Q, R
1, R
2, G
1, G
2and G
4as described in chemical formula (I), and X
15it is halogen.There is Formula I u
ccompound can with compound R
34-M
0(wherein M
0a kind of boric acid), react under a kind of existence of palladium catalyst, to provide the compound with Formula I u.Work as M
0when being a kind of boric acid, this reaction is normally under the existence of a kind of alkali (such as salt of wormwood, cesium carbonate or potassiumphosphate), in a kind of inert solvent (such as diox), optionally in presence of water, carry out under using the temperature of a kind of palladium (0) catalyzer (such as four (triphenylphosphines) close palladium) between 80 DEG C-120 DEG C.This kind of suzuki reaction has good precedent in the literature, and see such as Ma Suda (Masuda), keep straight on people such as (Naoyuki), WO2012133607.The compound with chemical formula XXXV and XXXVa can from having the compound of Formulae II by the method preparation such as shown in scheme 4.
scheme 4
In scheme 4; by known to a person of ordinary skill in the art and be described in such as C. expense in (Ferri); " organic synthesis (ReaktionenderOrganischenSynthese) "; GeorgThiemeVerlag, city of Stuttgart, 1978; method in 223rd page of ff; when reacting with N, O-dimethyl hydroxyl amine, a kind of acyl halide with Formulae II a is converted into Yin Leibu Wei (Weinreb) acid amides IIb.Then, according to method (the tetrahedron bulletin (TetrahedronLetters) 1981 of Yin Leibu (Weinreb), 22,3815-3818), Yin Leibu Wei (Weinreb) acid amides making to have Formulae II b with there is chemical formula R
35cH
2the Grignard reagent reaction of MgHal, to provide the compound with chemical formula XXXVb and XXXVa.The compound with chemical formula XXXVa and XXXVb is also by with having chemical formula R
35cH
2the Grignard reagent process of MgHal has the nitrile compound (wherein Q is as described in Formula I) of Formulae II c, acid hydrolysis is subsequently (as (Ferri) in taking at C., " organic synthesis (ReaktionenderOrganischenSynthese) ", GeorgThiemeVerlag, city of Stuttgart, described in 1978,223rd page of ff) prepare.
Such as bromine and the Hydrogen bromide mixture in acetic acid can be used (as at phosphorus, sulphur and silicon and coherent element (Phosphorus, SulfurandSiliconandtheRelatedElements), 2013, 188 (12), described in 1835-1844) or with such as cupric bromide (II), at a kind of inert solvent (such as chloroform, ethyl acetate etc.) (as at pharmaceutical chemistry magazine (J.Med.Chem.), 2013, 56 (1), described in 84-96) in by the halogenations with chemical formula XXXVa and XXXVb be the compound with chemical formula XXXV.Alternately, there is compound (the wherein R of chemical formula XXXV
35hydrogen) by a kind of inert solvent (such as diethyl ether), use a kind of haloid acid (such as Hydrogen bromide or hydrochloric acid) to process subsequently with diazomethane or trimethylsilyldiazomwhiche whiche process, directly prepare from the compound with Formulae II a.This class method is well-known in the literature, for example, see European pharmaceutical chemistry magazine (Eu.J.Med.Chem.), and 1987,22 (5), 457-62 and WO2009010455.
In a similar fashion, there is Formula I u
acompound
(wherein R
1, G
1, G
2as described in chemical formula (I), and G
5cR
34) by making the compound with chemical formula (XXXIVa),
(wherein R
1, G
1, G
2as described in chemical formula (I)) with react to prepare the compound with Formula I u like the compounds with chemical formula XXXV or XXXVa and prepare.Those skilled in the art will recognize that there is Formula I u
bcompound
Similarly by making to have the compound of chemical formula XXXIVb as above and there is compound (the wherein G of chemical formula XXXV or XXXVa
5cR
34) react to prepare.
(wherein A is A to have the compound of Formula I
2and G
5nitrogen) subgroup can be represented by the compound with Formula I v;
(wherein Q is group B
1, B
2, B
3, B
4, B
5, B
6, B
7, B
8, B
9or B
11in one, and R
1, R
2, G
1, G
2and G
4as described in Formula I), by making the compound with chemical formula XXXVI;
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I), and wherein X
08 -chemical formula OSO
2r
38halide ions or negatively charged ion) with a kind of compound with Formulae II a
(wherein X
0be a kind of halogen and Q is as defined above), optionally under a kind of existence of applicable alkali, carry out reacting preparing in a kind of inert solvent.
The above compound with chemical formula XXXIV can by amino dehalogenation, by making the compound with chemical formula XXXVII;
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I), and wherein X
09a kind of halogen or a leavings group OSO
2r
38) react prepare with the ammonia (gaseous state or water-based) as nucleophilic reagent.In a kind of suitable inert solvent, optionally can use amount or the pole excess of ammonia of equimolar amount in pressurizing vessel.This reaction can temperature between 0 and 200 DEG C, optionally to carry out under microwave irradiation.Ammonia equivalent can also be used, such as ammonium hydroxide NH4OH, ammonium acetate NH
4oAc, volatile salt (NH4) 2CO3 are as nitrogen source.
The compound with chemical formula XXXVII can by making to have the compound of chemical formula XXXVIII
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I)), in a kind of inert solvent, react with reagent such as phosphoryl chloride, phosphorus trichloride or phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide and prepare.
The compound with chemical formula XXVIII is known in the literature.Such as, there is compound (the wherein G of chemical formula XXXVIII
2be nitrogen-atoms and G
1cR
31, and wherein R
1and R
2as described in Formula I) in EP1371638 be known or can analogy its prepare.
The compound with chemical formula XXXVI can by N-amination, carry out reacting preparing with O-trimethylbenzenesulfonyl azanol (O-mesitylenesulfonylhydroxylamine) (MSH) as amination reagent by making the above compound with chemical formula XXXIV, as by people such as such as Y. Tian Cun (Tamura), heterocyclic chemistry magazine (J.HeterocyclicChem.) 1975, described in 12,107-110.Also known MSH is in the form of its precursor for its acetyl-hydroxamic acid ethyl ester; With the perchloric acid HClO in such as tetrahydrofuran (THF)
4the amination reagent MSH needed for pre-treatment release carried out.O-trimethylbenzenesulfonyl azanol (O-mesitylenesulfonyl-hydroxylamine) and relevant amination reagent are people such as Y. Tian Cun (Tamura), and synthesis (Synthesis), 1-17, summarizes in 1977.
(wherein A is A to have the compound of Formula I
3and G
5nitrogen) subgroup can be represented by the compound with Formula I w
Wherein Q is group B
1, B
2, B
3, B
4, B
5, B
6, B
7, B
8, B
9or B
11in one, and wherein R
1, R
2, G
1, G
2and G
4as described in Formula I.
Then, G is worked as
4cR
33time, there is the compound of Formula I w by making to have the compound of chemical formula XXXIX
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I)) and a kind of compound with chemical formula XL
(wherein X
10a kind of halogen or a leavings group OSO
2r
38, and Q is as defined above), optionally under a kind of existence of applicable alkali, react in a kind of inert solvent and prepare.
Alternately, G is worked as
4when being nitrogen, there is the compound of Formula I w by making to have the compound of chemical formula XLI
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I), and wherein X
11 -chemical formula OSO
2r
38halide ions or negatively charged ion) with a kind of compound with Formulae II a
(wherein X
0be a kind of halogen and Q is as defined above), optionally under a kind of existence of applicable alkali, react in a kind of inert solvent and prepare.
The above compound with chemical formula XXXIX can by amino dehalogenation, by making the compound with chemical formula XLII
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I), and wherein X
12a kind of halogen or a leavings group OSO
2r
38) react prepare with the ammonia (gaseous state or water-based) as nucleophilic reagent.In a kind of suitable inert solvent, optionally can use amount or the pole excess of ammonia of equimolar amount in pressurizing vessel.This reaction can temperature between 0 and 200 DEG C, optionally to carry out under microwave irradiation.Ammonia equivalent can also be used, such as ammonium hydroxide NH
4oH, ammonium acetate NH
4oAc and volatile salt (NH
4)
2cO
3as nitrogen source.
The compound with chemical formula XLII can by making to have the compound of chemical formula XLIII
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I)), in a kind of inert solvent, react with reagent such as phosphoryl chloride, phosphorus trichloride or phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide or thionyl chloride and prepare.
The compound with chemical formula XL can such as be prepared by analogy EP1371638.
The compound with chemical formula XLI can by N-amination, prepare, as described in previous compound preparation to chemical formula XXXVI with reacting as O-trimethylbenzenesulfonyl azanol (O-mesitylenesulfonylhydroxylamine) (MSH) of amination reagent or its a kind of equivalent by making the above compound with chemical formula XXXIX.
(wherein A is A to have the compound of Formula I
7and G
5and G
4both nitrogen) subgroup can be represented by the compound with Formula I x
Wherein Q is group B
1, B
2, B
3, B
4, B
5, B
6, B
7, B
8, B
9or B
11in one, and wherein R
1, R
2, G
1and G
2as described in Formula I.
The compound with Formula I c can by making to have the compound of chemical formula XLIV
(wherein R
1, R
2, G
1and G
2as described in chemical formula (I)) and a kind of compound with chemical formula XLV
X
13-Q(XLV)，
(wherein X
13a kind of halogen or a leavings group OSO
2r
38, and Q is as defined above, wherein group B
1, B
2, B
3, B
4, B
5, B
6, B
7, B
8, B
9or B
11in arrow display substituent X
13attachment point), optionally under a kind of existence of applicable alkali, analogy such as WO10/038081 reacts and prepares in a kind of inert solvent (sodium hydride such as in dimethyl formamide).
Alternately, the compound with Formula I x carries out reacting preparing with the compound with chemical formula XLV by the compound making to have chemical formula XLIV under the N-arylation condition of palladium chtalyst, as such as people such as S.L. Buchwalds (Buchwald), Germany's applied chemistry (Angew.Chem.Int.Ed.), 50,8944-8947, described in 2011.
The above compound with chemical formula XLIV can by diazotization, by the compound by having chemical formula XLVI
(wherein R
1, R
2, G
1and G
2as described in Formula I) with the Sodium Nitrite in water and haloid acid or use a kind of alkyl nitrite (such as nitrite tert-butyl or Isopentyl nitrite) in anhydrous conditions, optionally under a kind of existence of acid (such as acetic acid), in a kind of inert solvent (such as tetrahydrofuran (THF)), carry out processing at the temperature between 0 and 130 DEG C preparing.Can people such as figure Renyis (Torrini), heterocyclic chemistry magazine (J.HeterocyclicChem.), finds the representative instance relating to Isopentyl nitrite and acetic acid in the tetrahydrofuran (THF) of backflow in 23,1459-1463,1986.
There is compound (the wherein R of chemical formula (I)
21c
1-C
6alkene oxygen base ,-C (O) R
36) can as being prepared as shown in scheme 5, scheme 5 is for group A
1-B
1illustrate:
Scheme 5.
In scheme 5, there is compound (the wherein R of chemical formula XLVII
1, R
2, G
1, G
2, L
1, R
3, R
4, V
1and V
0as described in for chemical formula (I), and X
14halogen (preferably bromine)) with compound (the wherein R with chemical formula XLVIII
39to be selected from the monosubstituted or polysubstituted C of following substituting group
1-C
5alkyl: C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl, wherein said C
3-C
6it is monosubstituted or polysubstituted that cycloalkyl can be selected from the substituting group of lower group, and this group is by halogen and C
1-C
3alkyl forms; Or one can be selected from the monosubstituted or polysubstituted phenyl group of the substituting group of lower group, this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form), in a kind of inert solvent (such as THF, DMF, diox, octane, toluene and dimethylbenzene), at a kind of inert solvent (such as toluene and dimethylbenzene and DMF, or these a kind of mixture etc.) in a kind of palladium catalyst (such as tetrakis triphenylphosphine palladium (0) or two (triphenylphosphine) Palladous chloride (II)) existence under, react at the temperature (preferably 50 DEG C-90 DEG C) between 25 DEG C-120 DEG C.Then, the product X LIX obtained is processed under the existence of a kind of organic cosolvent (such as methyl alcohol, acetone, ethanol, THF etc.) with a kind of mineral acid (such as water-based hydrochloric acid), to provide product (the wherein substituent R with chemical formula 1y
1, R
2, G
1, G
2, L
1, R
3, R
4, V
1, V
0and R
39as the aforementioned).These processes are well-known, and previously such as little China fir (Kosugi), the people such as positive moral (Masanori), Chemical Society's publication of Japan (Bull.Chem.Soc.Japan), 60 (2), 767-8, describe in 1987.
Similar chemical process can be used to R
4, R
5, R
20, R
22, R
23, R
24, R
25, R
26, R
27, R
28, R
29, and R
30the so a kind of substituting group of middle introducing.
In many cases, in document, the known compound with Formulae II is commercially available or can be prepared by the method be similar to described in document.Such as 3-ethylsulfonyl-5-(trifluoromethyl) pyridine-2-carboxylic acids (WO2013180194), 3-ethylsulfonyl pyridine-2-carboxylic acids (WO2013180194), 3-ethylsulfonyl pyrazine-2-carboxylic acid (WO2013180194), (the synthesis (Synthesis) of 3-ethylsulfonyl thiophene-2-carboxylic acid, 2007, (12), 1827-1832), 3-ethylsulfonyl-5-(trifluoromethyl) thiophene-2-carboxylic acid (WO2013180193), the chloro-6-of 2-(trifluoromethyl) pyridine-3-carboxylic acid (WO2013180194), 5-Ethylsulfanyl thiazole-4-carboxylic acid (WO2013180193), 2-Ethylsulfanyl thiophene-3-carboxylic acid (WO2013180193), and the bromo-2-methyl isophthalic acid of 4-, 1-dioxo-2, 3-dihydrobenzo thiophene-7-carboxylic acid (WO199909023),
In other cases, the synthesis be developed particularly for the compound with Formulae II has the compound of Formula I with preparation, and shown in following scheme:
scheme 6.
scheme 7.
scheme 8
scheme 9
scheme 10
scheme 11:
scheme 12
Known in document there is Formulae II I, the compound of IV and V be commercially available maybe can by being similar to these the method preparation in document.Such as N-2-methyl-5-(trifluoromethyl) pyridine-2, 3-diamines (WO2012086848), 6-(trifluoromethyl) pyridine-3, 4-diamines (WO2013/048214), N-3-methyl-6-(trifluoromethyl) pyridine-2, 3-diamines (WO2012/086848), N-5-methyl-2-(trifluoromethyl) pyrimidine-4, 5-diamines (CAS [1023817-05-1]), N-1-methyl-4-(trifluoromethyl) benzene-1, 2-diamines (WO2005065680), 3-amino-5-(trifluoromethyl) pyridine-2-alcohol (WO2011049222), 3-amino-5-(trifluoromethyl)-2 (1H)-pyrithione (WO2011/043404).
In other cases, be developed particularly for having Formulae II I, the synthesis of compound of IV and V had the compound of Formula I with preparation, and shown in following scheme:
scheme 13
scheme 14
scheme 15:
scheme 16:
To have Formula I compound other synthesis shown in following scheme:
scheme 17.
scheme 18:
Exist a large amount of that be applicable to, known, for the preparation of the compound with chemical formula (I) of every other functionalization (according to A
1-A
6and B
1-B
11definition) standard method, as alkanisation, halogenation, acidylate, amidation, oximate, oxidation and reduction, the substituent characteristic (reactivity) in these intermediate products is depended in the selection of applicable preparation method.
These reactants can react under a kind of existence of alkali.The example of suitable alkali is basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal hydride, basic metal or alkaline earth metal amide, basic metal or alkaline-earth metal alcoholate, basic metal or alkaline earth metal acetates, basic metal or alkaline earth metal carbonate, basic metal or alkaline-earth metal dialkyl amide or basic metal or alkaline-earth metal alkylsilylamides, alkylamine, Alkylenediamine, free or the alkylating saturated or undersaturated Cycloalkyl amine of N-, basic heterocycles, ammonium oxyhydroxide and carbocyclic ring amine.The example that can mention is sodium hydroxide, sodium hydride, sodium amide, sodium methylate, sodium acetate, sodium carbonate, potassium tert.-butoxide, potassium hydroxide, salt of wormwood, potassium hydride KH, diisopropylamino lithium, two (TMS) acid amides potassium, hydrolith, triethylamine, diisopropylethylamine, triethylenediamine, hexahydroaniline, N-cyclohexyl-N, N dimethylamine, N, N-diethyl-aniline, pyridine, 4-(N, N-dimethylamino) pyridine, rubane, N-methylmorpholine, benzyltrimethylammon.um oxyhydroxide and 1, 8-diazabicylo [5.4.0] 11-7-alkene (DBU).
These reagent can react as it is each other, that is: need not add solvent or thinner.But in most of the cases, it is favourable for adding a kind of inert solvent or thinner or these mixture.If this reaction is carried out under a kind of existence of alkali, the alkali (as triethylamine, pyridine, N-methylmorpholine or N, N-diethyl-aniline) of so these excessive uses can also serve as solvent (or thinner).
This reaction advantageously from about-80 DEG C to about+140 DEG C, preferably from about-30 DEG C to about+100 DEG C, is carried out in many cases at the temperature between envrionment temperature and about+80 DEG C.
The compound with Formula I can be converted into itself known method a kind of the compound that another kind has Formula I, and this is by being realized with another or other one or more substituent substituting according to the present invention by these initial one or more substituting groups with the compound of Formula I in a usual manner.
Depend on reaction conditions and the parent material of selected applicable respective situation, likely such as, only a substituting group another substituting group according to the present invention is substituted in a reactions steps, or multiple other substituting groups according to the present invention of multiple substituting group can be substituted in same reactions steps.
The salt with these compounds of Formula I can be prepared in a way known.Therefore, such as, the acid salt with the compound of Formula I is by carrying out processing obtaining with a kind of applicable acid or a kind of suitable ion exchange reagent, and is by carrying out processing obtaining with a kind of applicable alkali or with a kind of suitable ion exchange reagent with the salt of alkali.
The salt with the compound of Formula I can be converted into free Compound I, acid salt (such as by processing with a kind of suitable basic cpd or with a kind of suitable ion exchange reagent) and alkali salt (such as by processing with a kind of suitable acid or with a kind of suitable ion exchange reagent) in a usual manner.
The salt with the compound of Formula I can be converted into other salt, the acid salt of the compound with Formula I in itself known mode a kind of, such as be transformed into other acid salt, such as pass through in a kind of suitable solvent with a kind of suitable metal-salt (such as a kind of sodium, barium or silver salt of acid, such as use silver acetate) process a kind of salt (such as hydrochloride) of mineral acid, in this solvent, a kind of inorganic salt (such as silver chloride) formed are insoluble and are therefore settled out from this reaction mixture.
Depend on this program or reaction conditions, there is salify characteristic these have Formula I compound can in a free form or the form of salt obtain.
Have Formula I compound and suitable time its tautomer (in free form or in salt form in each situation) can with the form of one of possible isomer or with the form of a kind of mixture of these isomer, such as with pure isomer (such as enantiomorph and/or diastereomer) form or such as, with isomer mixture (such as enantiomeric mixture, racemic modification; Non-enantiomer mixture or raceme mixture) form exists, depends on the number of the unsymmetrical carbon existed in molecule, absolute and relative configuration and/or depend on the configuration of the non-aromatic double bond existed in molecule; The present invention relates to pure isomer and possible all isomer mixtures, and in each situation contextual, even specifically do not mentioning in each situation of stereochemical details, all should understand from this layer of meaning.
The mixture (their acquisition can depend on selected parent material and program) of the non-enantiomer mixture with the compound of Formula I or racemic modification that are in free form or salt form on the basis of the physical chemical differences of these components, such as, can be separated into pure diastereomer or racemic modification by a kind of known method of fractional crystallization, distillation and/or chromatography.
The enantiomeric mixture (such as racemic modification) that can obtain with a kind of similar fashion can split into optical antipode by currently known methods, such as, pass through from a kind of optical activity solvent recrystallize; By the chromatography on chiral sorbent, such as, high performance liquid chromatography (HPLC) (HPLC) on cellulose acetate; By means of suitable microorganism, by using specific immobilised enzymes cracking; By formed inclusion compound, such as use chiral crown ether, wherein only an enantiomer by complexing; Or by changing into diastereo-isomerism salt, such as by making a kind of alkaline final product racemic modification and a kind of optical activity acid (such as carboxylic acid, such as camphor, tartrate or oxysuccinic acid or sulfonic acid, such as camphorsulfonic acid) reaction, and be separated the non-enantiomer mixture that can obtain in this way, such as pass through fractional crystallization based on its different solubilities, thus acquisition diastereomer, desired enantiomer can be made to become free by the effect of suitable reagent (such as alkaline reagents) from these diastereomers.
Pure diastereomer or enantiomerism physical efficiency obtain according to the present invention, be not only by being separated suitable isomer mixture, can also be the method for diastereoselectivity by generally known or enantioselective synthesis, such as, by utilizing a kind of suitable stereochemical parent material to carry out the method according to the present invention.
Can by there is the compound of Formula I and a kind of applicable oxygenant (such as H
2o
2/ urea complex) under acid anhydrides (such as, trifluoroacetic anhydride) exists, carry out reaction preparation N-oxide compound.This type of oxidation is from document, such as, known from pharmaceutical chemistry magazine (J.Med.Chem.) 1989,32,2561 or WO2000/15615.
If these independent components have different biological activitys, advantageously this biologically more effective isomer isolated or synthesized in each case, such as enantiomer or diastereomer, or isomer mixture, such as enantiomeric mixture or non-enantiomer mixture.
These have Formula I compound and suitably time its tautomer (being in free form or salt form in each case) can also obtain with the form of hydrate and/or comprise other solvent if appropriate, such as may be used for the crystallization of the compound existed in solid form those.
The compound with Formula I according to the present invention is have the activeconstituents preventing and/or treating value in harmful organism control field, even under low amount of application, they have very advantageously kills biological spectrum and is that warm blooded species, fish and plant are well tolerable.These activeconstituentss according to the present invention act on all or other etap individual of animal pest biology that is normal responsive and that also have anti-medicine (representative as insect or acarina).Kill insect or acaricidal activity according to activeconstituents of the present invention can directly displays itself, that is or immediately or only in the past after some times (such as between ecdysis) occur to destroy harmful organism; Or indirectly show, such as reduce and lay eggs and/or hatching rate, correspond to the excellent activity of the destructive rate (mortality ratio) of at least 50%.
The compound with Formula I can be used for resisting and controlling infecting of harmful organism (such as, mite, nematode and the mollusk pests) of insect pest (such as lepidopteran, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera) and other invertebrates.Insects, mite class, threadworms and mollusc are generically and collectively referred to as harmful organism hereinafter.These by use the compounds of this invention antagonism and the harmful organism controlled comprise those with agricultural (this term comprises the cultivation of the farm crop of food and fiber product), gardening and herding, pet, forestry and vegetables source (such as fruit, grain and timber) the relevant harmful organism of the storage of product; Those harmful organisms relevant with the infringement of man-made structures and the pathophoresis of humans and animals; And public hazards harmful organism (such as fly).
The example of the pest that can be controlled by the compound with Formula I is comprised: black peach aphid (aphid), cotten aphid (aphid), black bean aphid (aphid), Lygus Hahn (fleahopper), red cotton bug belongs to (fleahopper), Nilaparvata lugen (brown planthopper) (plant hopper), rice green leafhopper (leafhopper), Bemisia spp (smelly stinkbug), America stinkbug belongs to (smelly stinkbug), Leptocorisa spp belongs to (smelly stinkbug), Frankliniella occidentalis (thrips), Thrips (thrips), colorado potato bug (colorado potato bug), Mexico's cotton boll resembles (anthonomus grandis), kidney Aspidiotus belongs to (scale insect), Aleyrodes (aleyrodid), Bemisia tabaci (aleyrodid), European corn borer (European corn borer), sea spodoptera (cotton leafworm), Heliothis virescens (tobacco budworm), bollworm (bollworm), the real noctuid (bollworm) of paddy, cotton leaf roller (cotton leaf roller), large white butterfly (white butterfly), small cabbage moth (Plutellaxylostella) (small cabbage moth (Diamondbackmoth)), Agrotis (cutworm), striped rice borer (striped rice borer), African migratory locust (locust), Australia's pestilence locust (locust), root Galeruca (rootworm), panonychus ulmi (European red mite), Jie-Li enzyme-SQ (citrus red mite), T.urticae Koch (Tetranychus urticae), carmine spider mite (red spider), tangerine rues rust mite (phyllocoptruta oleivora), Polyphagotarsonemus latus Banks (the thin mite of tea), short whisker Acarapis (grape brevipalpus), boophilus microplus (Boophilus annulatus), Dermacentor variabilis (american dog tick), ctenocephalides felis (cat flea), Liriomyza (leaf miner), housefly (housefly), Aedes aegypti (mosquito), Anopheles (mosquito), Culex (mosquito), Lucilia (calliphorid), Groton bug (cockroach), periplaneta americana (cockroach), the rough Lian in east (cockroach), the termite (such as Australia's Cryptotermes) of Mastotermitidae, Kalotermitidae (such as new Cryptotermes), Rhinotermitidae (such as coptotermes formosanus of taiwan, yellow limb reticulitermes flavipe, eastern subterranean termite, Reticulitermes virginicus, west reticulitermes flavipe and Sang Te reticulitermes flavipe) and Termitidae (such as yellow ball termite (Globitermessulphureus)), Solenopsis geminata (fiery ant), monomorium pharaonis (little red ant), Damalinia and Linognathus (sting lice and suck lice), Meloidogyne (root knot nematode), ball Heterodera and Heterodera (Cyst nematode), Pratylenchidae belongs to (rotten nematode), Rhodophyllus (radopholus similes thorne), pulvinulus sword Turbatrix (oranges and tangerines nematode), haemonchus contortus (twisted mawworm), Caenorhabditis elegans (vinegar worm vinegar eel), trichostrongylus (gastrointestinal nematode) and reticulate pattern Agriolimax agrestis Linnaeus (slug).
More examples of above-mentioned harmful organism are:
From acarina, such as, descend hair Eriophyes (Acalitusspp.), acupuncture Eriophyes (Aculusspp), narrow Eriophyes (Acaricalusspp.), Genus Aceria (Aceriaspp.), Acarus siro (Acarussiro), Amblyomma (Amblyommaspp.), Argas (Argasspp.), Boophilus (Boophilusspp.), short whisker Acarapis (Brevipalpusspp.), Bryobia (Bryobiaspp), upper three joints Eriophyes (Calipitrimerusspp.), Chorioptes (Chorioptesspp.), Dermanyssus gallinae (Dermanyssusgallinae), Dermatophagoides (Dermatophagoidesspp), Eotetranychus (Eotetranychusspp), Eriophyes (Eriophyesspp.), half Tarsonemus (Hemitarsonemusspp), Hyalomma (Hyalommaspp.), hard tick belongs to (Ixodesspp.), Oligonychus (Olygonychusspp), Ornithodoros (Ornithodorosspp.), Polyphagotarsonemus latus Banks (Polyphagotarsonelatus), Panonychus citri belongs to (Panonychusspp.), tangerine rues rust mite (Phyllocoptrutaoleivora), herbivore mite (Phytonemusspp.), Tarsonemus (Polyphagotarsonemusspp), Psoroptes (Psoroptesspp.), Rh (Rhipicephalusspp.), Rhizoglyphus (Rhizoglyphusspp.), itch mite belongs to (Sarcoptesspp.), Steneotarsonemus (Steneotarsonemusspp), instep line belongs to (Tarsonemusspp.) and Tetranychus (Tetranychusspp.),
From Anoplura, such as Haematopinus (Haematopinusspp.), Linognathus (Linognathusspp.), Pediculus (Pediculusspp.), Pemphigus (Pemphigusspp.) and Psylla spp (Phylloxeraspp.);
From Coleoptera, such as, lack grand click beetle and belong to (Agriotesspp.), European chafer (Amphimallon majalis) (Amphimallonmajale), east different beetle (Anomalaorientalis), flower resembles genus (Anthonomusspp.), Aphodius (Aphodiusspp), leather winged beetle (Astylusatromaculatus) intended by corn, cockchafer belongs to (Ataeniusspp), Atomaria linearis (Atomarialinearis), beet shin flea beetle (Chaetocnematibialis), Galeruca (Cerotomaspp), single leaf click beetle belongs to (Conoderusspp), collar resembles genus (Cosmopolitesspp.), green gold tortoise (Cotinisnitida), Curculio (Curculiospp.), round end rhinoceros cockchafer belongs to (Cyclocephalaspp), round end rhinoceros cockchafer belongs to (Dermestesspp.), root Galeruca (Diabroticaspp.), Argentina's pocket worm (Diloboderusabderus), epilachna genus (Epilachnaspp.), Eremnusspp., black different pawl sugarcane cockchafer (Heteronychusarator), coffee berryborer (Hypothenemushampei), Lagriavilosa, colorado potato bug (LeptinotarsadecemLineata), rice water resembles genus (Lissorhoptrusspp.), Liogenysspp, Maecolaspisspp, maroon suede cockchafer (Maladeracastanea), Megascelisspp, Melighetesaeneus, cockchafer belongs to (Melolonthaspp.), Myochrousarmatus, saw-toothed grain beetle belongs to (Orycaephilusspp.), ear beak resembles genus (Otiorhynchusspp.), Phyllophaga (Phyllophagaspp), spot resembles genus (Phlyctinusspp.), rutelian belongs to (Popilliaspp.), rape phyllotreta (Psylliodesspp.), Rhyssomatusaubtilis, Rhizopertha (Rhizoperthaspp.), Scarabaeidae (Scarabeidae), Sitophilus (Sitophilusspp.), gelechiid belongs to (Sitotrogaspp.), pseudo-cutworm belongs to (Somaticusspp), point Rhynchophorus (Sphenophorusspp), soybean stem resembles (Sternechussubsignatus), Tenebrio (Tenebriospp.), Tribolium (Triboliumspp.) and spot khapra beetle belong to (Trogodermaspp.),
From Diptera, such as Aedes (Aedesspp.), Anopheles (Anophelesspp), jowar awns fly (Antherigonasoccata.), olive fruit trypetid (Bactroceaoleae), garden march fly (Bibiohortulanus), Bradysia Sciara (Bradysiaspp.), calliphora erythrocephala (Calliphoraerythrocephala), little bar Anastrepha (Ceratitisspp.), Carysomyia (Chrysomyiaspp.), Culex (Culexspp.), Cuterebra (Cuterebraspp.), few hair on the neck Anastrepha (Dacusspp.), Delia (Deliaspp), drosophila melanogaster (Drosophilamelanogaster), Fannia (Fanniaspp.), Gasterophilus (Gastrophilusspp.), Geomyzatripunctata, Glossina (Glossinaspp.), Hypoderma (Hypodermaspp.), Hippobosca (Hyppoboscaspp.), Liriomyza (Liriomyzaspp.), Lucilia (Luciliaspp.), Hippelates (Melanagromyzaspp.), Musca (Muscaspp.), Oestrus (Oestrusspp.), cecidomyiia belongs to (Orseoliaspp.), Oscinella frit (Oscinellafrit), lamb's-quarters spring fly (Pegomyiahyoscyami), Phorbia (Phorbiaspp.), around Anastrepha (Rhagoletisspp), Riveliaquadrifasciata, Scatellaspp, Sciara (Sciaraspp.), Stomoxys (Stomoxysspp.), Gadfly (Tabanusspp.), tapeworm belongs to (Tanniaspp.) and large uranotaenia (Tipulaspp.),
From Hemiptera, such as knurl coried (Acanthocorisscabrator), Bemisia spp, alfalfa plant bug, Amblypeltanitida, sea shrimp shield coried (Bathycoeliathalassina), chinch bug belongs to soil, Cimex, Clavigrallatomentosicollis, fleahopper belongs to (Creontiadesspp.), Distantiella theobroma, Dichelopsfurcatus, red cotton bug belongs to, Edessaspp, America stinkbug belongs to (Euchistusspp.), six spot cabbage bugs (Eurydemapulchrum), Eurygasterspp belongs to, eating attraction, the recessed huge section chief stinkbug (Horciasnobilellus) of tool, Leptocorisa spp belongs to (Leptocorisaspp.), Lygus Hahn, the large a red-spotted lizard in the torrid zone belongs to, harlequin bug (Murgantiahistrionic), new long coried belongs to (Neomegalotomusspp), cigarette fleahopper (Nesidiocoristenuis), Bemisia spp, intend chinch bug (Nysiussimulans), island stinkbug (Oebalusinsularis), skin stinkbug belongs to, wall stinkbug belongs to, Rhodnius, cocoa mirid pentatomid, chestnut soil stinkbug (Scaptocoriscastanea), black stinkbug belongs to (Scotinopharaspp.), Thyantaspp, cone nose Eimeria, cassava lace bug (Vatigailludens), without net long tube Aphis, Adalgesspp, Agallianaensigera, the lucky Nimu lice (Agonoscenatargionii) difficult to understand of tal fibre, Aleyrodes (Aleurodicusspp.), thorn Aleyrodes (Aleurocanthusspp), sugarcane cave aleyrodid, fur aleyrodid (Aleurothrixusfloccosus), wild cabbage aleyrodid (Aleyrodesbrassicae), chlorita biguttula (Amarascabiguttula), the long prominent leafhopper (Amritodusatkinson) of mango, kidney Aspidiotus belongs to, Aphidiadae, Aphis, a red-spotted lizard belongs to (Aspidiotusspp.), eggplant ditch is without net aphid, potato wood louse (Bactericeracockerelli), little Aleyrodes, short-tail Aphis (Brachycaudusspp), brevicoryne brassicae, noise made in coughing or vomiting Psylla spp, two tail aphid (CavariellaaegopodiiScop.), lecanium belongs to, brown round a red-spotted lizard, net seed blade of grass circle a red-spotted lizard, cicadellid belongs to (Cicadellaspp), great Bai leafhopper (Cofanaspectra), hidden tumor aphid genus, leafhopper belongs to (Cicadulinaspp), Coccushesperidum, maize wing leafhopper, naked Aleyrodes, diaphorina citri, Diuraphis noxia, western rounded tail Aphis, Empoasca flavescens, eriosoma lanigerum, grape leafhopper belongs to, wax clam belongs to, eucalyptus camaldulensis wood louse (Glycaspisbrimblecombei), turnip aphid, large tail Aphis (Hyalopterusspp), super knurl aphid kind, mango greenery cicada (Idioscopusclypealis), Africa leafhopper (Jacobiascalybica), small brown rice planthopper belongs to, the hard a red-spotted lizard of ball, lepidosaphes shimer, radish aphid (Lopaphiserysimi), Lyogenysmaidis, long tube Aphis, froghopper belongs to (Mahanarvaspp), Flatidae (Metcalfapruinosa), wheat is without net aphid, Mynduscrudus, tumor aphid genus, Taiwan fragrant-flowered garlic aphid, rice green leafhopper belongs to, brown paddy plant hopper belongs to (Nilaparvataspp.), the large greenbug of pears, Bermuda grass trifle shell worm (Odonaspisruthae), parasitic sugar cane cottony aphid, red bayberry edge aleyrodid, Kao Shi wood louse, Parlatoria, Pemphigus, com planthopper, flat angle plant hopper belongs to, phorodon aphid, Phylloxera spp, Planococcus, white armored scale belongs to, mealybug belongs to, cotton plant bug (Pseudatomoscelisseriatus), Psylla spp, cotton a red-spotted lizard (Pulvinariaaethiopica), large bamboo hat with a conical crown and broad brim Aspidiotus belongs to, Quesadagigas, recilia dorsalis (Reciliadorsalis), Rhopalosiphum, black bourch belongs to, Scaphoideus, y-bend Aphis, wheat aphid belongs to (Sitobionspp.), white backed planthopper, triangle clover springtail (Spissistilusfestinus), streak plant hopper (TarophagusProserpina), sound Aphis, Aleyrodes, Tridiscussporoboli, certain herbaceous plants with big flowers mealybug belongs to (Trionymusspp.), Africa wood louse, tangerine arrowhead scales, flame Erythroneura spp (Zyginaflammigera), Zyginidiascutellaris,
From Hemiptera, such as Cimex, the blind honeybee of cocoa knurl, red cotton bug genus, America stinkbug genus, Eurygasterspp genus, Leptocorisa spp belong to (Leptocorisaspp.), Bemisia spp, plan lace bug genus, Rhodnius, Sahlbergella singularis (Scotinopharaspp.), black stinkbug genus and Triatoma;
From Homoptera, such as fur aleyrodid, dish aleyrodid, kidney Aspidiotus belongs to, Aphidiadae, Aphis, thin targe shell Eimeria (Aspidiotusspp.), Bemisia tabaci, lecanium belongs to, dark brown Aspidiotus, Chrysomphalus ficus, Coccushesperidum, Empoasca spp belongs to, apple aphid, Erythroneura spp belongs to, wax clam belongs to, small brown rice planthopper belongs to, the hard a red-spotted lizard of water and soil, Lepidosaphes, long tube Aphis, tumor aphid genus, rice green leafhopper belongs to, brown paddy plant hopper belongs to, Parlatoria, Pemphigus, Planococcus (Planococcusspp.), intend white wheel shield shell Eimeria, mealybug belongs to, Psylla spp, cotton a red-spotted lizard, tooth armored scale belongs to, Rhopalosiphum, pearl lecanium belongs to, Scaphoideus, y-bend Aphis, wheat aphid belongs to, Trialeurodes vaporariorum Westwood, Africa wood louse and citrus point shield rank,
From Hymenoptera, such as push up Myrmecina (Acromyrmex), three joints tenthredinidae (Argespp.), Bu Qieye Cryptotermes (Attaspp.), stem tenthredinidae (Cephusspp.), Diprion (Diprionspp.), Diprionidae (Diprionidae), pine sawfoy (Gilpiniapolytoma), pear fruit sawfly belongs to (Hoplocampaspp.), hair ant belongs to (Lasiusspp.), monomorium pharaonis (Monomoriumpharaonis), Neodiprion (Neodiprionspp.), agriculture ant belongs to (Pogonomyrmexspp), red fire ant (Slenopsisinvicta), Solenopsis (Solenopsisspp.) and Vespa (Vespaspp.),
From Isoptera, such as formosanes belongs to (Coptotermesspp), termite (Corniternescumulans), principal columns of a hall Cryptotermes (Incisitermesspp), Macrotermes (Macrotermesspp), Australia's Cryptotermes (Mastotermesspp), little Cryptotermes (Microtermesspp), Reticulitermes (Reticulitermesspp.); Solenopsis geminata (Solenopsisgeminate);
From lepidopteran, such as Acleris spp belongs to (Aclerisspp.), Adoxophyes spp belongs to (Adoxophyesspp.), clearwing moth belongs to (Aegeriaspp.), ground Noctua (Agrotisspp.), cotton leafworm (Alabamaargillaceae), starch Eimeria (Amyloisspp.), Anticarsia (Anticarsiagemmatalis), Archips spp (Archipsspp.), silver moth belongs to (Argyresthiaspp.), Argyrotaenia spp belongs to (Argyrotaeniaspp.), gamma belongs to (Autographaspp.), cotton lyonetid (Bucculatrixthurberiella), corn pattern noctuid (Busseolafusca), amyloid plaque snout moth (Cadracautella), peach fruit moth (Carposinanipponensis), straw borer spp (Chilospp.), leaf roller belongs to (Choristoneuraspp.), more climing tangerine crambid (Chrysoteuchiatopiaria), grape codling moth (Clysia ambiguella) (Clysiaambiguella), leaf roll snout moth's larva belongs to (Cnaphalocrocisspp.), cloud volume moth belongs to (Cnephasiaspp.), line volume moth belongs to (Cochylisspp.), casebearer moth (Coleophoraspp.), hedge bean powder butterfly (Coliaslesbia), Cosmophilaflava, Crambus Fabricius (Crambusspp), large Oeobia undalis (Crocidolomiabinotalis), Cryptophlebia leucotreta (Cryptophlebialeucotreta), Ramulus Buxi Sinicae moth (Cydalimaperspectalis), moth-eaten moth belongs to (Cydiaspp.), Diaphania perspectalis (Diaphaniaperspectalis), bar Crambus Fabricius (Diatraeaspp.), the Sudan bollworm (Diparopsiscastanea), Earias (Eariasspp.), dehydrated sweet potato snout moth's larva (Eldanasaccharina), meal moth belongs to (Ephestiaspp.), leaf steinernema belongs to (Epinotiaspp), salt pool moths attracted by lamplight (Estigmeneacrea), bean-pod borer (Etiellazinckinella), flower steinernema belongs to (Eucosmaspp.), ring pin list line moth (Eupoeciliaambiguella), Euproctis (Euproctisspp.), cut Noctua (Euxoaspp.), Feltiajaculiferia, Grapholita (Gra-pholitaspp.), malachite worm moth (Hedyanubiferana), Heliothis (Heliothisspp.), Oeobia undalis (Hellulaundalis), wild snout moth's larva belongs to (Herpetogrammaspp), fall webworms (Hyphantriacunea), the moth-eaten moth (Keiferialycopersicella) of tomato, Corn snout moth's larva (Lasmopalpuslignosellus), apple leaf-miner (Leucopterascitella), the thin moth of leaf mining belongs to (Lithocollethisspp.), grape flower wing steinernema (Lobesiabotrana), Loxostegebifidalis, Euproctis (Lymantriaspp.), lyonetid belongs to (Lyonetiaspp.), curtain Lasiocampa (Malacosomaspp.), lopper worm (Mamestrabrassicae), maduca sexta (Manducasexta), secret Noctua (Mythimnaspp), Noctua (Noctuaspp), autumn geometrid moth genus (Operophteraspp.), Orniodesindica, Pyrausta nubilalis (Hubern)., super steinernema belongs to (Pammenespp.), brown epiblema (Pandemisspp.), small noctuid (Panolisflammea), common moth stem noctuid (Papaipemanebris), Pectinophora gossypiella (Pectinophoragossypiela), coffee leafminer (Perileucopteracoffeella), America mythimna separata (Pseudaletiaunipuncta), potato tuberworm (Phthorimaeaoperculella), pieris rapae (Pierisrapae), dish miller belongs to (Pierisspp.), small cabbage moth (Plutellaxylostella), little Bai Yponomeuta (Praysspp.), chi Noctua (Pseudoplusiaspp), peppermint ash noctuid (Rachiplusianu), beans ground, west fragrant (Richiaalbicosta), white standing grain snout moth's larva belongs to (Scirpophagaspp.), moth stem Noctua (Sesamiaspp.), long palpus volume moth belongs to (Sparganothisspp.), Spodoptera (Spodopteraspp.), cotton leaf roller (Syleptaderogate), Synanthedon (Synanthedonspp.), different boat pretty young woman belongs to (Thaumetopoeaspp.), leaf roller belongs to (Tortrixspp.), cabbage looper (Trichoplusiani), tomato gelechiid (Tutaabsoluta), and Yponomeuta (Yponomeutaspp.),
From Mallophaga, such as,
Damalinia and Trichodectes;
From Orthoptera, such as Lian genus, Blatella, Gryllotalpa spp, leucophaea maderae, migratory locusts genus, northern mole cricket (Neocurtillahexadactyla), Periplaneta, mole cricket spp (Scapteriscusspp) and desert locust belong to;
From Corrodentia, such as lice nibbles genus (Liposcelisspp.);
From Siphonaptera, such as Ceratophyllus (Ceratophyllusspp.), Ct (Ctenocephalidesspp.) and Xanthopsyllacheopis (Xenopsyllacheopis);
From Thysanoptera, such as,
Calliothripsphaseoli, flower thrips belong to (Frankliniellaspp.), Heliothrips (Heliothripsspp), brown Taeniothrips (Hercinothripsspp.), single parent's Thrips (Parthenothripsspp.), the hard thrips of aurantiin (Scirtothripsaurantii), soybean thrips (Sericothripsvariabilis), Taeniothrips (Taeniothripsspp.), Thrips (Thripsspp); And
From Thysanura, such as silverfish (Lepismasaccharina).
Activeconstituents according to the present invention can be used for the harmful organism controlling, namely contain or destroy the above-mentioned type; these harmful organisms appear on plant especially; especially on the useful plant in agricultural, in gardening and in forestry and ornamental plant; or on the organ of these plants; such as fruit, flower, leaf, stem, stem tuber or root; and the plant organ in some cases, even formed at a time point subsequently still keeps these harmful organisms of protected opposing.
Suitable target crop specifically cereal, such as wheat, barley, rye, oat, paddy rice, corn or Chinese sorghum; Beet, such as sugar beet or fodder beet; Fruit, such as apple class fruit, stone fruit or pitted fruit, such as apple, pears, plum, peach, almond, cherry or berry, such as strawberry, raspberry or blackberry, blueberry; Leguminous crop, such as broad bean, root of Szemao crotalaria, pea or soybean; Oil crops, such as rape, leaf mustard, opium poppy, olive, Sunflower Receptacle, coconut, castor-oil plant, cocoa or Semen arachidis hypogaeae; Cucurbit, such as pumpkin, cucumber or muskmelon; Textile plant, such as cotton, flax, hemp or jute; Citrus fruits, such as orange, lemon, natsudaidai or orange; Vegetables, such as spinach, lettuce, asparagus, wild cabbage, Radix Dauci Sativae, onion, tomato, potato or bell pepper; Canella, such as avocado, Chinese cassia tree or camphor; And also have tobacco, nut, coffee, eggplant, sugarcane, tealeaves, pepper, grapevine, hops, Plantaginaceae, rubber yielding plant and ornamental plant.
In yet another aspect, the present invention also can relate to control by phytotrophy nematode (entozoic-, half entozoic-and ectoparasitic nematode) plant or its part are caused to a kind of method of infringement, the nematode of especially following phytotrophy, as root knot nematode (rootknotnematodes), M hapla (Meloidogynehapla), Meloidogyne incognita (Meloidogyneincognita), javanese root knot nematode (Meloidogynejavanica), peanut root-knot nematode (Meloidogynearenaria) and other Meloidogyne kinds (Meloidogynespecies), sporangiocyst forms nematode (cyst-formingnematodes), globodera rostochiensis (Globoderarostochiensis) and other ball cyst roundworms and belongs to kind (Globoderaspecies), cereal cyst nematode (Heteroderaavenae), soybean cyst nematode Heterodera glycines (Heteroderaglycines), beet Cyst nematode (Heteroderaschachtii), red clover golden nematode (Heteroderatrifolii) and other Heterodera kinds (Heteroderaspecies), plant goitre nematode (Seedgallnematodes), grain Turbatrix kind (Anguinaspecies), stem and blade face nematode (Stemandfoliarnematodes), Aphelenchoides kind (Aphelenchoidesspecies), seta nematode (Stingnematodes), long-tail thorn nematode (Belonolaimuslongicaudatus) and other thorn Turbatrix kinds, pine wilt nematode (Pinenematodes), pine wood nematode (Bursaphelenchusxylophilus) and other Bursaphelenchus kinds (Bursaphelenchusspecies), annular nematode (Ringnematodes), loop wire Eimeria kind (Criconemaspecies), little loop wire Eimeria kind (Criconemellaspecies), Criconemoides kind (Criconemoidesspecies), Middle Ring Line Eimeria kind (Mesocriconemaspecies), stem and lepisphere Ditylenchus dipsaci (Stemandbulbnematodes), rot stem nematodes (Ditylenchusdestructor), Ditylenchus dip saci (Ditylenchusdipsaci) and other Ditylenchus kinds (Ditylenchusspecies), cone nematode (Awlnematodes), cone Turbatrix kind (Dolichodorusspecies), helicotylenchus (Spiralnematodes), multi-head spiral nematode (Heliocotylenchusmulticinctus) and other spiral-line Eimeria kinds (Helicotylenchusspecies), sheath and sheath shape nematode (Sheathandsheathoidnematodes), sheath Turbatrix kind (Hemicycliophoraspecies) and half Criconemoides kind (Hemicriconemoidesspecies), Hirschmanniella kind (Hirshmanniellaspecies), prop up nematode (Lancenematodes), Stephanurus kind (Hoploaimusspecies), false root knot nematode (falserootknotnematodes), pearl curve Eimeria kind (Nacobbusspecies), needle-like nematode (Needlenematodes), cross band minute hand nematode (Longidoruselongatus) and other minute hand Turbatrix kinds (Longidorusspecies), pin nematode (Pinnematodes), Pratylenchidae belong to kind (Pratylenchusspecies), rotten nematode (Lesionnematodes), piebald Pratylenchidae (Pratylenchusneglectus), Cobb root (Pratylenchuspenetrans), bending Pratylenchidae (Pratylenchuscurvitatus), Gooch Pratylenchidae (Pratylenchusgoodeyi) and other Pratylenchidaes belong to kind (Pratylenchusspecies), citrus similes thorne (Burrowingnematodes), radopholus similes thorne (Radopholussimilis) and other radopholus belong to kind (Radopholusspecies), spiral nematode (Rotylenchusrobustus), kidney shape of kidney shape nematode (Reniformnematodes), sieve Bai Shi is spiraled nematode (Rotylenchusreniformis) and other Turbatrix kinds (Rotylenchusspecies) of spiraling, shield Turbatrix kind (Scutellonemaspecies), short and thick nematode (Stubbyrootnematodes), original burr nematode (Trichodorusprimitivus) and other burr Turbatrix kinds (Trichodorusspecies), plan burr Turbatrix kind (Paratrichodorusspecies), species of Tylenchorhynchus Nematodes (Stuntnematodes), purslane species of Tylenchorhynchus Nematodes (Tylenchorhynchusclaytoni), suitable inverse species of Tylenchorhynchus Nematodes (Tylenchorhynchusdubius) and other Tylenchorhynchus kinds (Tylenchorhynchusspecies), citrus nematode (Citrusnematodes), puncture Turbatrix kind (Tylenchulusspecies), dirk nematode (Daggernematodes), Xiphinema kind (Xiphinemaspecies), and the line insect types of other plant parasitism, as sub-grain Turbatrix (Subanguinaspp.), Hypsoperine belongs to, large coronule Turbatrix (Macroposthoniaspp.), Melinius belong to, punctum cyst belongs to (Punctoderaspp.) and five ditch Turbatrixs (Quinisulciusspp.).
These compounds of the present invention also have for molluscan activity.These molluscan examples comprise, such as apple Cionellidae; A Yong Limax (Arion) (greyish black A Yong slug (A.ater), ring spot A Yong slug (A.circumscriptus), garden A Yong slug (A.hortensis), reddish brown A Yong slug (A.rufus)); Bradybaenidae (shrub bar snail (Bradybaenafruticum)); Cepaea (garden snail (C.hortensis), forest snail (C.nemoralis)); Ochlodina; Ash Limax (Deroceras) (wild grey slug (D.agrestis), D.empiricorum, field ash slug (D.laeve), flower garden ash slug (D.reticulatum)); Disk spiral shell belongs to (Discus) (D.rotundatus); Euomphalia; Soil snail belongs to (Galba) (cutting shape soil snail (G.trunculata)); Little Cepaea (Helicelia) (the little snail of IITTALA (H.itala), cloth tie up little snail (H.obvia)); Helicidae Helicigonaarbustorum); Helicodiscus; Helicella (Helix) (open helix (H.aperta)); Limax (Limax) (greyish black slug (L.cinereoniger), yellow slug (L.flavus), edge slug (L.marginatus), large slug (L.maximus), soft slug (L.tenellus)); Lymnaea (Lymnaea); Milax (M.gagates, M.marginatus, M.sowerbyi); Auger shell belongs to (Opeas); Bottle spiral shell belongs to (Pomacea) (P.canaticulata); Vallonia (Vallonia) and Zanitoides.
Term " crop " should be understood to that the result also comprised as conventional breeding methods or gene engineering method has become weedicide (as bromoxynil) or classes of herbicides (such as HPPD inhibitor, ALS inhibitor, such as primisulfuronmethyl, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphoric acid-synthetic enzyme) inhibitor, GS (glutamine synthetase) inhibitor) there is the crop of tolerance.The example become imidazolone such as imazamox has a crop of tolerance by conventional breeding methods (mutagenesis) is
summer rape (Kano is drawn (Canola)).Be endowed due to genetic engineering method and glyphosate and careless fourth phosphine resistant corn kind comprised to the example of the crop of multiple weedicide or multiple other tolerance of classes of herbicides, they
with
commercially available under trade name.
Term " crop " will also be understood that as also comprising the crop plants that can synthesize one or more selectively acting toxin by using recombinant DNA technology to carry out transforming, these toxin are such as known, such as from toxogenic bacterium, those of especially bacillus.
Such as insecticidal protein can be comprised, such as, from the insecticidal protein of bacillus cereus or Japanese beetle genus bacillus by the toxin of these Expressed in Transgenic Plants; Or from the insecticidal protein of bacillus thuringiensis, such as delta-endotoxin, such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c, or vegetative phase insecticidal protein (VIP), such as VIP1, VIP2, VIP3 or VIP3A; Or the insecticidal protein of bacterial clone nematode, such as Photorhabdus or Xenorhabdus, such as luminous bacillus, Xenorhabdus nematophilus; The toxin produced by animal, such as scorpion toxin, spider venom, wasp toxin and other insect-specific neurotoxins; By mycetogenetic toxin, such as streptomycete toxin; Phytohemagglutinin, such as pea hemoglutinin, barley hemoglutinin or snowdrop hemoglutinin; Lectin; Proteinase inhibitor, such as trypsin inhibitor, serpin, stem tuber storage protein, cystatin, antipain; Ribosome inactivating protein (RIP), such as Ricin, corn-RIP, abrin, sponge gourd toxin, saporin or red bryony toxalbumin; Steroid metabolism enzyme, such as 3-hydroxy steroid oxydase, the solid acid-UDP-glycosyl-transferring enzyme of class of casting off a skin, rCO, moulting hormone inhibitor, HMG-COA-reductase enzyme, ion channel blocking agent, the blocker of such as sodium channel or calcium channel, juvenile hormone esterase, diuretic hormone acceptor, stilbene synthase, bibenzyl synthases, chitinase and dextranase.
In the context of the present invention, delta-endotoxin, such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c, or vegetative phase insecticidal protein (VIP), such as VIP1, VIP2, VIP3 or VIP3A should be interpreted as it is also hybridization toxin, truncated toxins and modification toxin clearly.Mixed type toxin is (such as, see, WO02/15701) that produced by the restructuring of the Combination nova of the different zones of those albumen.Truncated toxins, such as brachymemma CryIA (b) is known.When modified toxin, one or more amino acid of naturally occurring toxin are replaced.In these amino-acid substitutions, to not be preferably that naturally occurring protease recognition sequence is inserted in toxin, such as when CryIIIA055, kethepsin-D-recognition sequence is inserted in a CryIIIA toxin (see WO03/018810).
The example that such toxin maybe can synthesize the transgenic plant of such toxin is disclosed in such as EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO03/052073.
Be known for the preparation of the method for such transgenic plant for those of ordinary skill in the art and be described in such as above-mentioned publication.CryI-type thymus nucleic acid and preparation example thereof are as known from WO95/34656, EP-A-0367474, EP-A-0401979 and WO90/13651.
The toxin be included in transgenic plant makes plant have tolerance to harmful insect.These insects may reside in any classification of insect group, but especially usual discovery in beetle (Coleoptera), dipteran (Diptera) and butterfly (lepidopteran).
Comprise one or more encodes biocide resistance and the transgenic plant of expressing the gene of one or more toxin are known and some of them are commercially available.The example of such plant is:
(corn variety expresses CryIA (b) toxin); YieldGard
(corn variety expresses CryIIIB (b1) toxin); YieldGard
(corn variety expresses CryIA (b) and CryIIIB (b1) toxin);
(corn variety expresses Cry9 (c) toxin); Herculex
(corn variety is expressed CryIF (a2) toxin and is realized the enzyme phosphinothricin N acetyl transferring enzyme (PAT) of the tolerance to weedicide grass fourth phosphine ammonium); NuCOTN
(cotton variety expresses CryIA (c) toxin); Bollgard
(cotton variety expresses CryIA (c) toxin); Bollgard
(cotton variety expresses CryIA (c) and CryIIA (b) toxin);
(cotton variety expresses VIP toxin);
(Potato Cultivars expresses CryIIIA toxin);
gTAdvantage (GA21 glyphosate tolerant proterties),
cBAdvantage (Bt11 Pyrausta nubilalis (Hubern). (CB) proterties) and
Other examples of such genetically modified crops are:
1.Bt11 corn, from Xian Zhengda seeds company (SyngentaSeedsSAS), Huo Bitelu (Chemindel ' Hobit) 27, F-31790 Sheng Suweier (St.Sauveur), France, registration number C/FR/96/05/10.The Zea mays of genetic modification, by CryIA (b) toxin of transgene expression brachymemma, makes it the invasion and attack of resisting European corn borer (Pyrausta nubilalis (Hubern). and powder stem snout moth's larva).Bt11 corn also transgenosis ground expresses PAT enzyme to reach the tolerance to weedicide grass fourth phosphine ammonium salt.
2.Bt176 corn, from Xian Zhengda seeds company (SyngentaSeedsSAS), Huo Bitelu (Chemindel ' Hobit) 27, F-31790 Sheng Suweier (St.Sauveur), France, registration number C/FR/96/05/10.The Zea mays of genetic modification, by transgene expression CryIA (b) toxin, makes it the invasion and attack of resisting European corn borer (Pyrausta nubilalis (Hubern). and powder stem snout moth's larva).Bt176 corn also transgenosis ground expresses PAT enzyme to reach the tolerance to weedicide grass fourth phosphine ammonium salt.
3.MIR604 corn, from Xian Zhengda seeds company (SyngentaSeedsSAS), and Huo Bitelu (Chemindel ' Hobit) 27, F-31790 Sheng Suweier (St.Sauveur), France, registration number C/FR/96/05/10.The corn of anti-insect has been become by the CryIIIA toxin that transgene expression is modified.This toxin is the Cry3A055 modified by inserting a cathepsin-D-protease recognition sequence.The preparation of such rotaring gene corn plant is described in WO03/018810.
4.MON863 corn, from Meng Shan all European Company (MonsantoEuropeS.A.), 270-272 Te Fulun main road (AvenuedeTervuren), B-1150 Brussels, Belgium, registration number C/DE/02/9.MON863 expresses CryIIIB (b1) toxin, and has resistance to some coleopteron.
5.IPC531 cotton, from Monsanto Company 270-272 Te Fulun main road (AvenuedeTervuren), B-1150 Brussels, Belgium, registration number C/ES/96/02.
6.1507 corns, from pioneer Worldwide, Inc (PioneerOverseasCorporation) (Belgium, Brussels, Tedesco main road (AvenueTedesco), 7B-1160), registration number C/NL/00/10.The corn of genetic modification, marking protein Cry1F is to realize the resistance of some lepidopterous insects and to express PAT protein to realize the tolerance to weedicide grass fourth phosphine ammonium salt.
7.NK603 × MON810 corn, from Meng Shan all European Company (MonsantoEuropeS.A.), 270-272 De Tewenrui street (AvenuedeTervuren), B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.By by the kind NK603 of genetic modification and MON810 hybridization, be made up of the hybrid corn variety of conventional breeding.NK603 × MON810 corn gene expresses the CP4EPSPS protein obtained by Agrobacterium strains CP4, makes it herbicide-resistant
(containing glyphosate), and CryIA (b) toxin obtained by B. thuringiensis subspecies, make it some lepidopterous insects resistance to, comprise European corn borer.
The genetically modified crops of anti-insect plant are also described in BATS (Zentrumf ü rBiosicherheitundNachhaltigkeit, ZentrumBATS, Clarastrasse13,4058 Basels, Switzerland) and report in 2003.
Term " crop " is appreciated that also to comprise and is transformed by using recombinant DNA technology the crop can synthesizing the antipathogen with selectively acting like this, these antipathogens are so-called " pathogenesis-related proteins " (PRP, see such as EP-A-0392225) such as.The example of this type of antipathogen and the transgenic plant that can synthesize this type of antipathogen is such as known from EP-A-0392225, WO95/33818 and EP-A-0353191.The method of producing these type of transgenic plant for those skilled in the art normally known and be described in such as above-mentioned publication.
Can be comprised by the anti-material caused a disease of such Expressed in Transgenic Plant, such as ion channel blocking agent, as the blocker of sodium and calcium channel, the such as KP1 of virus, KP4 or KP6 toxin; Stilbene synthase, bibenzyl synthases; Chitinase; Dextranase; So-called " pathogenesis-related protein " (PRP, see such as EP-A-0392225); By the anti-material caused a disease that microorganism produces, the skin antibiotics such as, related in plant pathogen defence or heterocyclic antibiotics class (see such as WO95/33818) or protein or polypeptide factor (so-called " Plant Genes Conferring Resistance To Pathogens ", as described in WO03/000906).
Crop also can be modified with the resistance increased fungi (mould, the anthrax of such as reaping hook or phytophthora), bacterium (such as pseudomonas) or virus (such as corium solani, tomato spotted wilf virus, cucumber mosaic virus) pathogenic agent.
Crop also comprises the crop that those have the resistance of the increase to nematode (as soybean cyst nematode).
Have and those such as have the tolerance of the increase to arid, high salt, high temperature, cold, frost or optical radiation crop by NF-YB or other protein expressions as known in the art is comprised to the crop of the tolerance of abiotic stress.
The crop of the output or quality that represent increase comprises those and has blooming of improvement or fruit maturation characteristic (such as delayed maturity); Modified oil, starch, amino acid, lipid acid, VITAMIN, phenols or other inclusion (such as Wei Sidifu (Vistive)
tMsoybean varieties); Strengthen nutrien utilization (such as improveing nitrogen assimilation); And strengthen the plant product cotton fibre of high-quality (such as more) of quality.
Be goods stored by protection and storage room according to other use fields of compound of the present invention and composition and protect starting material; such as timber, textiles, floor or buildings; and in hygiene department, especially protect the mankind, harmful organism that the livestock of domestic animal and fecund exempts from mentioned type.
Present invention also offers a kind of for controlling harmful organism (as Dulicidae and other Disease carrier; See also http://www.who.int/malaria/vector_control/irs/en/) method.In one embodiment, the method for controlling harmful organism comprises by brushing, rolling, spraying, coating or dipping, to this object noxious livings, they place surface or matrix use composition of the present invention.By way of example, the IRS (indoor residual spray) contemplating a kind of surface (e.g., wall, top ceiling or floor surface) by method of the present invention uses.In another embodiment, take into account and such composition is applied to a kind of matrix, as nonwoven or textile material, this material is in the form (or may be used for using in the manufacture of these article) of mesh, serving, bed clothes, curtain and tent.
In one embodiment, method for controlling this type of harmful organism comprises uses a kind of composition of the present invention killing harmful organism significant quantity to this object noxious livings, their place or surface or matrix so that effective delay is provided on this surface or matrix kill harmful organism activity.This type of is used and or can flood and of the present inventionly kill harmful organism composition to carry out by brushing, rolling, spraying, coating.By way of example, the IRS that method of the present invention contemplates a kind of surface (e.g., wall, top ceiling or floor surface) uses so that provide on a surface effective be detained kill harmful organism activity.In another embodiment, contemplate and use the control of such composition for the delay of the harmful organism in a kind of matrix, this matrix is the textile material of the form (or may be used for using in the manufacture of these article) being such as in mesh, serving, bed clothes, curtain and tent.
There is pending matrix (comprising non-woven fleece, fabric or mesh) can by natural fiber, as, cotton, rufiyaa leaf fiber, jute, flax, sisal hemp, sack cloth or wool, or synthon, as polymeric amide, polyester, polypropylene, polyacrylonitrile etc. are made.Polyester is particularly suitable.The method of textile treatment is known, such as WO2008/151984, WO2003/034823, US5631072, WO2005/64072, WO2006/128870, EP1724392, WO2005113886 or WO2007/090739.
For the fruit tree of all ornamental trees together with all kinds and the tree injection/trunk process field of nutwood according to other scopes of the purposes of these compositions of the present invention.
In tree injection/trunk process field, these compounds according to the present invention are particularly suitable for resisting from above-mentioned lepidopteran and the brill wood insect from Coleoptera, especially resist the brill carpenter worm of listing in following table AA and BB:
table A A. has the example of the external brill carpenter worm of Economic Importance.
table BB. has the example of this ground auger carpenter worm of Economic Importance.
In hygiene department, be for ectoparasite according to compound of the present invention and composition, such as hard tick, soft ticks, itch mite, harvest mite, fly (sting and lick), tachinid larva, lice, head louse, bird lice and flea are effective.
This type of parasitic example is:
Anoplura: Haematopinus, long palate lice genus, Pediculus and Pthirus, pipe lice belong to.
Mallophaga: hair Trichodectes, short angle bird lice genus, duck lice genus, Bovicola, Werneckiella genus, Lepikentron genus, Damalinia, Trichodectes and Felicola.
Diptera and Nemocera and Brachycera, such as Aedes, Anopheles, Culex, Simulium, Eusimulium, owl midge, Lutzomyia, Bitting midge, Chrysops, Hybomitra, Atylotus, Gadfly, Chrysozona, Philipomyiaspp., honeybee Hippobosca, Musca, Hydrotaea, Genus Stomoxys, Haematobia, not fly genus, Fannia, Glossina, Calliphora, Lucilia, Carysomyia, Wohlfahrtia, Sarcophaga, Oestrus, Hypoderma, Gasterophilus, Hippobosca, Lipoptena and Melophagus.
Siphonaptera, such as flea genus, Ct, objective flea genus, Ceratophyllus.
Heteroptera, such as Cimex, Triatoma, Rhodnius, Triatoma.
Blattodea, such as oriental cockroach, periplaneta americana, Groton bug and Supella.
Acari (mite section) and rear valve order and Mesostigmata, such as Argas, Ornithodoros, Otiobius, hard tick genuss, Amblyomma, Boophilus, Dermacentor, Haemaphysalis, Hyalomma, Rh, Dermanyssus, thorn profit mite genuss, Pneumonyssus, chest sting mite genus and Varroa.
Axle Acarina (front valve suborder) and flour mite order (Astigmata), such as, under honeybee shield mite genus, Ji chela genus, Ornithocheyletia, Myobia, Psorergates, Demodex, Trombidium, yak mite genus, Tyroglyphus, Tyrophagus, Caloglyphus, neck mite genus, wing mite genus, Psoroptes, Chorioptes, ear itch mite genus, itch mite genus, Notoedres, Knemidokoptes, Cytoleichus and Laminosioptes.
Describedly also be applicable to protecting materials if timber, textiles, plastics, tackiness agent, glue, paint vehicle, paper and card, leather, floor and building etc. are from insect infestations according to these compounds of the present invention and composition.
Composition according to the present invention may be used for such as resisting following harmful organism: beetle, such as North America house longhorn beetle, the longicorn that becomes mildewed, furniture death watch beetle, red hair death watch beetle, Ptilinus pectinicornis, the stem of noble dendrobium, loose bud branch death watch beetle, loose product death watch beetle, Lyctus brunneus Stephens, moth-eaten, the southern powder of African powder is moth-eaten, quercitron is moth-eaten, pubescence powder moth, chest powder moth, minthea rugicollis, material bark beetle belongs to, wood strip bark beetle belongs to, black long moth-eaten, long moth-eaten, the brown different wing length moth of tree of coffee, Sinoxylon and dinoderus minutus; And hymenopterans insect, such as blue-black wood wasp, the large wood wasp of dragon spruce, Urocerus gigas toiganus and large wood wasp; And termite, such as European kalotermitid, numb head heap sand termite, the different termite of Indian-Pakistani structural wood, eastern subterranean termite, Sang Te reticulitermes flavipe, reticulitermes flavipe, Mastotermes darwiniensis, the ancient termite in Nevada and Coptotermes formosanus Shtrari．; And moth, such as silverfish.
Therefore, the invention provides a kind of insecticidal, kill mite, nematicide or kill molluscan composition, preferably insecticidal or kill the composition of mite, said composition comprise insecticidal, kill mite, nematicide or kill the compound with Formula I of molluscan significant quantity and a kind of to its suitable carrier or thinner.
In other at one, the invention provides a kind of method of antagonism and control harmful organism, the method comprises killing insect, kills mite, nematicide or kill mollusk significant quantity, preferably kill insect and the compound with Formula I that kills mite significant quantity or a kind of composition of comprising the compound with Formula I is applied to harmful organism, place, harmful organism place, or be applied to the plant being subject to pest infestation, except a kind of by operation or therapy for the treatment of except the method for human body or animal body and the diagnostic method implemented human body or animal body.
The compound with Formula I is preferred for antagonism insect or mite.
Term as used herein " plant " comprises seedling, shrub and trees.
The invention still further relates to one and kill harmful organism composition, said composition, except comprising this compound with Formula I, also comprises multiple preparation adjuvant.
Therefore the present invention also relates to and kills harmful organism composition; emulsifiable concentrate such as in polymeric agents, suspension-concentrates, directly can spray or dilutable solution, the paste that can smear, dilute emulsion, soluble powder, dispersible powder, wettable powder, dust, particle or encapsulation, these kill harmful organism composition and comprise according at least one in activeconstituents of the present invention and be selected to applicable set objective and prevailing circumstances.
In these compositions, activeconstituents adopts in a pure form, solid active agent such as in a concrete granularity, or preferably together with at least one in the auxiliary agent used routinely in preparation field, these auxiliary agents such as extender, such as solvent or solid carrier, or such as surface active cpd (tensio-active agent).
The example of suitable solvent is: unhydrided or partially hydrogenated aromatic hydrocarbons, preferably C8 to the C12 part of alkylbenzene, such as xylene mixture, alkylated naphthalene or tetraline, aliphatics or cycloaliphatic hydrocarbon, such as paraffin or hexanaphthene; Alcohol, such as ethanol, propyl alcohol or butanols; Glycol and its ether and ester, such as propylene glycol, dipropylene glycol, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; Ketone, such as pimelinketone, isophorone or diacetone alcohol; Intensive polar solvent, such as NMP, methyl-sulphoxide or DMF, water; Non-epoxidation or epoxidized vegetable oil, such as non-epoxidation or epoxidized oil rapeseed oil, Viscotrol C, Oleum Cocois or soybean oil and organic silicone oil.
For such as dirt agent and dispersible powder solid carrier normally through the natural mineral of grinding, such as calcite, talcum, kaolin, montmorillonite or attapulgite.In order to improve physical properties, the interpolation silica of high dispersing or the absorbable polymer of high dispersing are also possible.Suitable particulate adsorptive support for granule is multi-hole type, such as float stone, brick gravel, sepiolite or wilkinite, and suitable non-sorptive carrier materials is calcite or sand.In addition, inorganic or the particulate material, particularly rhombspar of organic natural goods or the vegetable remains material of pulverizing in a large number can be used.
Depend on the type of activeconstituents to be prepared, suitable surface active cpd is non-ionic type, cationic and/or aniorfic surfactant or surfactant mixture, and they have good emulsifying, dispersion and wet characteristic.The tensio-active agent below mentioned only is considered as example; That use routinely in preparation field and be described in pertinent literature according to other tensio-active agents a large amount of that the present invention is suitable for.
The polyglycol ether derivative of suitable nonionic surface active agent especially aliphatics or cycloaliphatic alcohol, saturated or unsaturated fatty acids or alkylphenol, these derivatives can comprise about 3 to about 30 ethylene glycol ether groups and about 8 to about 20 carbon atoms in (ring) aliphatic hydrocarbon groups or about 6 to about 18 carbon atoms in the moieties at alkylphenol.Also the adducts of it is suitable that water-soluble polyethylene oxide and polypropylene glycol, second diamino polypropylene glycol or alkyl polypropylene glycol, these adductss have 1 to about 10 carbon atom in alkyl chain and about 20 to about 250 ethylene glycol ether groups and about 10 to about 100 propylene glycol ether groups.Usually, each propylene glycol units of above-claimed cpd comprises 1 to about 5 ethylene glycol unit.The example that can mention is nonylphenoxy polyethoxy ethanol, Viscotrol C polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributyl phenoxypolyethoxy ethanols, polyoxyethylene glycol or octylphenoxy polyethoxy ethanol.The also fatty acid ester of desirably polyoxy ethene anhydro sorbitol, such as polyethenoxy sorbitan trioleate.
Cationic surfactant have especially generally at least one alkyl residue (about 8 to about 22 C atoms) alternatively base and (non-halogenation or halogenation) low alkyl group or hydroxyalkyl or benzyl residue as further substituent quaternary ammonium salt.These salt are preferably in the form of halogenide, Methylsulfate or sulfovinate.Example is two (2-chloroethyl) the ethyl phosphonium bromide ammonium of stearyl trimethyl ammonium chloride and benzyl.
The example of suitable aniorfic surfactant is the surface active cpd of water-soluble soap class or water-soluble synthesis.The example of suitable soap class has about 10 an alkali metal salts to the lipid acid of about 22 C atoms, alkaline earth salt or (unsubstituted or be substituted) ammonium salt, such as oleic acid or stearic sodium salt or sylvite or such as from sodium salt or the sylvite of coconut or the obtainable natural acid mixture of Yatall MA; Also must it is mentioned that fatty acid methyltaurinates.But, the benzimidizole derivatives of the tensio-active agent more usually synthesized, particularly Fatty sulphonates, fat sulphate, sulfonation or alkylaryl sulphonate.Usually, Fatty sulphonates and fat sulphate are with the existence of an alkali metal salt, alkaline earth salt or (substituted or unsubstituted) ammonium salts and these salt have about 8 alkyl to about 22 C atoms generally, and alkyl is also construed as the moieties comprising acyl group; The example that can mention is lignosulfonic acid, laurilsulfate or the sodium salt of fatty alcohol sulphuric acid ester mixture prepared from natural acid or calcium salt.This group also comprises thioesters salt and the sulfonate of fatty alcohol/ethylene oxide adduct.The benzimidizole derivatives of these sulfonation preferably comprises 2 alkylsulfonyls and has the fatty acid residue of about 8 to about 22 C atoms.The example of alkylaryl sulphonate is the sodium of decylbenzenesulfonic acid, dibutyl naphthalenesulfonic acid or naphthene sulfonic acid/formaldehyde condensation products, calcium or tri ethanol ammonium salt.In addition, the phosphoric acid salt be also possibly applicable to, the phosphate ester salt of such as nonylphenol/(4-14) ethylene oxide adduct, or phosphatide salt.The phosphoric acid ester be applicable in addition is three esters of phosphoric acid and aliphatics or aromatic alcohols and/or the diester of alkylphosphonic acid carboxylic acid and aliphatics or aromatic alcohols, and the two is all efficient oil type adjuvant.These three esters to be described in such as WO01/47356, WO00/56146, EP-A-0579052 or EP-A-1018299 or commercially available under its chemical name.Preferably phosphoric acid three ester for these novel compositions is tricresyl phosphate-(2-ethylhexyl) ester, tricresyl phosphate n-octyl and three butoxy ethyl ester of phosphoric acid, and wherein tricresyl phosphate-(2-ethylhexyl) ester is most preferred.Suitable alkyl phosphonic acid dibasic acid esters be phosphonic acids two-(2-ethylhexyl)-(2-ethylhexyl) ester, phosphonic acids be two-two (2-the ethylhexyl)-Sanya propyl diester of (2-ethylhexyl)-(n-octyl) ester, phosphonic acids dibutyl-butyl ester and phosphonic acids, wherein phosphonic acids two-(2-ethylhexyl)-(n-octyl)-ester is particularly preferred.
Preferably can additionally comprise a kind of additive according to these compositions of the present invention, this additive comprises the mixture of the oil of plant origin or animal-origin, mineral oil, the alkyl ester of these oil or these oil and oily derivative.The value of the oil additive used in composition according to the present invention is 0.01% to 10% of this spraying mixture generally.For example, after this spraying mixture is prepared, this oil additive can be added in spray tank with desired concentration.Preferred oil additive comprises the oil of mineral oil or plant origin, and such as rapeseed oil (such as
and
), sweet oil or sunflower seed oil, the vegetables oil of emulsification, such as
(Luo Na-Planck Canada Company (
canadaInc.)), the alkyl ester of the oil of plant origin, such as methyl-derivatives, or the oil of animal-origin, such as fish oil or tallow.A kind of preferred additive-package containing such as by weight substantially 80% fish oil alkyl ester and by weight 15% the rapeseed oil and also have the conventional emulsifying agent of by weight 5% and pH to change agent as active ingredient of methylating.Especially preferred oil additive comprises C
8-C
22the alkyl ester of lipid acid, especially C
12-C
18the methyl-derivatives of lipid acid, the methyl ester of such as importantly lauric acid, palmitinic acid and oleic acid.Those esters are called as Laurate methyl (CAS-111-82-0), Uniphat A60 (CAS-112-39-0) and Witconol 2301 (CAS-112-62-9).A kind of preferred fatty acid methyl ester derivative is
2230 and 2231 (Kening Co., Ltd (CognisGmbH)).Those and other oily derivative is also known in weedicide adjuvant outline (CompendiumofHerbicideAdjuvants), the 5th edition, southern University of Illinois, 2000.In addition, alkoxylated fatty acid can be used as the additive in the present composition as the additive based on polymethyl siloxane, described by having had in WO2008/037373 based on the additive of polymethyl siloxane.
The application of these oil additives and effect can by by them and surfactants, such as non-ionic type, anionic or cationic surfactant combination and improving further.Be applicable to negatively charged ion, nonionic and cats product example WO97/34485 the 7th and 8 pages list.Preferred surfactant is the anion surfactant of dodecane benzyl sulphonate type, especially its calcium salt, and also has the nonionogenic tenside of fatty alcohol ethoxylate type.Particularly preferably be the C that ethoxylation degree is 5 to 40
12-C
22fatty alcohol.The example of commercially available tensio-active agent is Genapol type (the special company (ClariantAG) of Clariant).Further preferably organic silicon surfactant, the heptamethyltrisiloxane of especially poly-alkyl-oxide compound-modification, it is commercially available, such as, be Silwet
and fluoridized tensio-active agent.The relative concentration of surfactant in total body additives be from 1% to 30% generally by weight.The example of the oil additives be made up of the mixture of oils or mineral oil or derivatives thereof and tensio-active agent is EdenorME
(Syngenta Co., Ltd (SyngentaAG, CH)) and
(BP petroleum naphtha Co., Ltd (BPOilUKLimited, GB)).
Described surfactant can also be used in separately in preparation, that is without oil additive.
In addition, in this oil additive/surfactant mixture, add a kind of organic solvent and can contribute to further enhancement.The solvent be applicable to is such as
and Aromatic solvent (ESSO)
(Exxon Corporation (ExxonCorporation)).The concentration by weight of this kind solvent can be gross weight from 10% to 80%.This kind of oil additive can with solvent, and to describe in such as US-A-4834908.The name of a kind of commercially available oil additive wherein disclosed is called
(BASF AG (BASFCorporation)).According to the preferred another kind of oil additive of the present invention be
(first just reaching Crop protection branch office of Canada (SyngentaCropProtectionCanada)).
Except these oil additives listed above, in order to strengthen the activity according to these compositions of the present invention, also likely by alkyl pyrrolidone (such as
) preparation join in this spraying mixture.(such as polyacrylamide, polyvinyl compound or poly-1-p-menthene are (such as can also to use synthetic latex
or
)) preparation.Comprise the solution of propionic acid, such as Eurogkem
also may be mixed in in this spraying mixture as active reinforcing agent.
Term " activeconstituents " refers to the one had in these compounds of Formula I, the especially special compound with Formula I disclosed in these tables.It also refers to have the compound (particularly a kind of compound be selected from described table 1) of Formula I and the mixture of other insecticides, mycocide, weedicide, safener, adjuvant etc., and these mixtures are concrete as disclosed by following.
These compositions can also comprise other solids or liquid adjuvants, such as stablizer, such as non-epoxidation or epoxidized vegetable oil (such as epoxidised coconut oil, rapeseed oil or soybean oil); Defoamer, such as organic silicone oil; Sanitas; Viscosity modifier; Bonding agent and/or tackifier; Fertilizer, especially formulation fertilizer containing nitrogen, such as, ammonium nitrate as described in WO2008/017388 and urea, these fertilizer can strengthen effect of the compounds of this invention; Or for realizing other activeconstituentss of specific function, such as ammonium salt Huo phosphonium salt, especially halogenide, sulfuric acid (hydrogen) salt, nitrate, carbonic acid (hydrogen) salt, Citrate trianion, tartrate, formate and acetate, as described in WO2007/068427 and WO2007/068428, these salt also can strengthen effect of the compounds of this invention and can combinationally use with the penetration enhancer of such as alkoxylated fatty acid; Bactericide, mycocide, nematocides, activating plants agent, invertebrate poison or weedicide.
Composition according to the present invention is in itself known mode a kind of, when there is not auxiliary agent, such as, by grinding, screening and/or compression solid activeconstituents; Under existing at least one auxiliary agent, such as, grind activeconstituents to prepare by tight mixed active composition and a kind of or some auxiliary agents and/or together with a kind of or some auxiliary agents.
The application process of these compositions, namely be the method for the harmful organism controlling the above-mentioned type, as spraying, atomization, dusting, brush, dressing, broadcast sowing or water-they are selected to be suitable for the expection object-of common situation and these compositions are other themes of the present invention for controlling the purposes of the harmful organism of the above-mentioned type.Typical concentration ratio, between 0.1ppm and 1000ppm, is preferably the activeconstituents between 0.1ppm and 500ppm.
In Crop protection field, preferred application process is the leaf (foliar spray medicine) being applied to these plants, likely selects the frequency used and ratio to infect risk with what meet mentioned harmful organism.Alternately, this activeconstituents can be united by root system (systemic action) arrive plant, this is by be soaked in the location of these plants with a kind of liquid composition or by being realized in the location (such as introducing soil, such as, with the form of particle (soil is executed)) of the activeconstituents introduced plant of solid form.When rice crop, such granule can add in the rice field of waterflooding measuredly.
The protection (such as seed, as fruit, stem tuber or seed, or nursery plants) that these compositions according to the present invention are also suitable for plant propagation material resists the harmful organism of the above-mentioned type.This reproductive material can process before planting with these compositions, and such as seed can process prior to seeding.Alternately, these compositions can be applied to seed benevolence (coating), or by soaking these benevolence or pass through to be coated with one deck solids composition in liquid composition.When this reproductive material be planted in use place time, also such as during drilling, these compositions may be applied seeded furrow.These treatment processs of plant propagation material and comprising if the plant propagation material with a kind of compound of chemical formula (I) defined above is other themes of the present invention.
Comprise instillation according to other application process of these compositions of the present invention and be administered to soil, the part of dipped plants, such as ball stem or stem tuber, soak into soil and soil injection.These methods are that in this area, oneself knows.
In order to as insecticide, miticide, nematocides or invertebrate poison use there is Formula I compound to a kind of harmful organism, the place, a place of harmful organism or be administered to the kind of plant being subject to a kind of pest infestation, the compound with Formula I is formulated into a kind of composition usually, said composition is except comprising this compound with Formula I, also comprise a kind of suitable inert diluent or carrier, and optionally, a kind of preparation adjuvant in tensio-active agent (SFA) form described in EP-B-1062217 as the described herein or such as.SFA is can by reducing interfacial tension amendment interface (such as liquid/solid, liquid/gas or liquid/liquid interface) characteristic and the chemical that changes of other characteristics that cause thus (such as disperse, emulsification and moistening).
Under normal circumstances, these compositions comprise the activeconstituents of the Formula I of 0.1% to 99% (especially 0.1% to 95%) and at least one solid of 1% to 99.9% (especially 5% to 99.9%) or liquid adjuvant, and likely 0 to 25% (especially 0.1% to 20%) of said composition is tensio-active agent (% represents weight percent in each case) in principle.Although for commodity, concentrated composition is normally preferred, and terminal user uses the diluted composition of the activeconstituents with lower concentration in fact usually.
Typical concentration amount is between 0.1 and 1000ppm, the activeconstituents preferably between 0.1 and 500ppm.The amount of application of every public item is that every public item 1 arrives 2000g activeconstituents generally, especially 10 arrives 1000g/ha, preferably 10 arrives 600g/ha.
When using in a kind of seed dressing, have the compound of Formula I with every kilogram of seed 0.0001g to 10g (such as 0.001g or 0.05g), preferred 0.005g to 10g, more preferably the ratio of 0.005g to 4g uses.
The premixed goods of preferred seed treatment are aqueous suspension enriched materials.This preparation can use conventional treatment technology and machine, and such as fluidization, cylinder Ginding process, static rotation (rotostatic) subprocessors and rotary drum dressing device are administered on seed.Additive method, such as spouted bed also can be useful.These seeds can carry out pre-classification before dressing.After dressing, these seeds are typically carried out drying and then transfer in a starching machine being used for starching (sizing).Such method is known in the art.
These compositions can be selected from multiple preparation type, comprising can dirt powder (DP), soluble powder (SP), water-soluble granular (SG), water dispersibles particle (WG), wettable powder (WP), particle (GR) (slowly or fast discharging), solubility enriched material (SL), the mixable liquid of oil (OL), ultra low volume liquids (UL), emulsifiable concentrate (EC), dispersible enriched material (DC), emulsion (oil-in-water (EW) and water-in-oil (EO) both), microemulsion (ME), suspension-concentrates (SC), based on the suspension-concentrates (OD) of oil, aerosol, mist formation/smog preparation, capsule suspension liquid (CS) and seed treatment preparation.Under any circumstance, selected preparation type will depend on contemplated specific purposes and have the physics of compound of Formula I, chemistry and biological nature.
Can dirt pulvis (DP) compound and one or more solid diluents (such as, natural clay, kaolin, pyrophyllite, wilkinite, aluminum oxide, montmorillonite, diatomite (kieselguhr), chalk soil, diatomite (diatomaceousearths), calcium phosphate, calcium carbonate and magnesiumcarbonate, sulphur, lime, flour, talcum and other organic and inorganic solid carriers) with Formula I can be passed through to mix and this mixture is mechanically milled into fine powder to prepare.
Soluble powder (SP) can by by the compound with Formula I and one or more water-soluble inorganic salts (as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (as polysaccharide) and optionally one or more wetting agents, one or more dispersion agents or as described in the mixture of reagent carry out mixing and prepare to improve water dispersible/water-soluble.Then this mixture is ground to form fine powder.Also can by similar composition grain to form water-soluble granular (SG).
Wettable powder (WP) can by having the compound of Formula I and one or more solid diluents or carrier, one or more wetting agents and preferably, one or more dispersion agents, and preferably, the dispersion promoted in a liquid is prepared in one or more suspension agent mixing.Then this mixture is ground to form fine powder.Also can by similar composition grain to form water-dispersible granular material (WG).
Granule (GR) can be formed like this: by being formed by the mixture pelleting of the compound and one or more powdered solid diluents or carrier with Formula I, or by the compound (or its solution) in a kind of Suitable agents with Formula I is absorbed into honeycombed grain material (such as float stone, attapulgite clay, Fuller's earth, diatomite (kieselguhr), diatomite (diatomaceousearths) or corn cob meal), or it is (such as husky by the compound (or its solution) in Suitable agents with Formula I is adsorbed onto hard core material, silicate, mineral carbonic acid salt, vitriol or phosphoric acid salt) and if the words of upper necessity, carry out the preformed blank granules of dry cause to be formed.Generally comprise solvent (such as aliphatics and aromatic petroleum solvent, alcohol, ether, ketone and ester) and tackiness agent (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugar and vegetables oil) with the reagent of helping absorb or adsorb.Also one or more other additives (such as emulsifying agent, wetting agent or dispersion agent) can be comprised at particle.
Dispersibility enriched material (DC) can by preparing in water-soluble for the compound with Formula I or a kind of organic solvent (as ketone, alcohol or glycol ether).These solution can comprise tensio-active agent (being such as used for improving water-dilutable or prevent crystallization in spray cistern).
Emulsifiable concentrate (EC) or O/w emulsion (EW) can be prepared by being dissolved in a kind of organic solvent (optionally comprising the mixture of one or more wetting agents, one or more emulsifying agents or described reagent) by the compound with Formula I.The organic solvent class being suitable for EC comprises aromatic hydrocarbons, and (as alkyl benzene or alkylnaphthalene class, example is SOLVESSO100, SOLVESSO150 and SOLVESSO200; SOLVESSO is a registered trademark), ketone (as pimelinketone or methylcyclohexanone) and alcohol (as benzyl alcohol, furfuryl alcohol or butanols),
The dimethylformamide class of N-alkyl pyrrolidine ketone (as N-Methyl pyrrolidone or NOP), lipid acid is (as C
8-C
10fatty acid dimethylamides) and chlorinated hydrocarbon.EC product can the spontaneously emulsification when being added in water, produces and have enough stability to allow to spray by suitable equipment the emulsion used.The preparation of EW relates to acquisition as a kind of liquid (if it is not at room temperature liquid, then it can melt under typically lower than the reasonable temperature of 70 DEG C) or be in the compound with Formula I of (by it being dissolved in suitable solvent) in solution, then under high shear gained liquid or emulsifying soln are entered to comprise in the water of one or more SFA, to produce emulsion.The solvent be applicable to used in EW comprise vegetables oil, chlorinated hydrocarbon (as chlorobenzene), aromatic solvent (as alkylbenzene or alkylnaphthalene) and other there is the suitable organic solvent of low solubility in water.
Microemulsion (ME) can be prepared by mix by the adulterant of water and one or more solvents and one or more SFA, spontaneously to produce the thermodynamically stable isotropic liquid formulations of one.The compound with Formula I is present in water or in solvent/SFA adulterant at the very start.Use in ME be applicable to solvent comprise previously described use in EC or EW those.ME can be oil-in-water system or water-in-oil system (there is which kind of system to be determined by conductivity measurement) and can be suitable in identical preparation, mix water miscible and oil-soluble pesticides.ME is suitable for dilution and enters in water, remains microemulsion or forms conventional O/w emulsion.
Suspension-concentrates (SC) can comprise a kind of water-based or the non-aqueous suspensions with the insoluble solids particle of the fine dispersion of the compound of Formula I.SC can by by the solid chemical compound with Formula I optionally with one or more dispersion agents in appropriate medium ball milling or pearl grind to prepare, to produce the fine particle suspension of this compound.One or more wetting agents can be comprised in the composition, and suspension agent can be comprised to reduce the settling velocity of particle.Alternately, can to dry grind the compound with Formula I and added in the water comprising previously described reagent, to produce the final product of hope.
Oil-based suspension enriched material (OD) can be prepared similarly by being suspended in a kind of organic fluid (such as at least one mineral oil or vegetables oil) by the insoluble solid particle with the compound of Formula I of fine dispersion.OD can comprise at least one penetration enhancers (such as a kind of alcohol ethoxylate or a kind of related compound), at least one nonionic surface active agent and/or at least one aniorfic surfactant further, and optionally at least one is from the additive of lower group, this group has emulsifying agent, froth suppressor, sanitas, antioxidant, dyestuff and/or inert fill material.OD is wanted and is applicable to dilute with water before the use to produce a kind of spray solution with enough stability, thus allows to carry out sprinkling by suitable equipment and use.
Aerosol formulations comprises the compound with Formula I and the propelling agent (such as, normal butane) be applicable to.Also the compound with Formula I can be dissolved in or be scattered in applicable medium (such as water or can be miscible with a kind of water liquid, as n-propyl alcohol) in be provided in the composition used in non-pressurized spread by hand pump.
The compound with Formula I can mix with firework mixture to form a kind of composition being applicable to produce in enclosed space the smog comprising described compound in the dry state.
Capsule suspension liquid (CS) can by preparing in the mode similar with preparation EW preparation, except additional polymerization procedure, make like this to obtain the water dispersion of oil droplet, wherein each oil droplet is wrapped up by polymer shell and containing a kind of compound and its optional a kind of carrier or the thinner with Formula I.This polymer shell can be reacted by interfacial polycondensation or be produced by cohesion program.These compositions can provide this and have the controlled release of the compound of Formula I and they may be used for seed treatment.The compound with Formula I also can be formulated in biodegradable polymeric matrix, to provide the controlled release slowly of this compound.
The compound with Formula I can also be formulated to use as seed treatment, such as powder composition, comprise for the powder (DS) of dry method seed treatment, water miscible powder (SS) or for the dispersible powder of water (WS) of slurry process or as a kind of liquid composition, comprise flowable enriched material (FS), a kind of solution (LS) or a kind of capsule suspension liquid (CS).The preparation of DS, SS, WS, FS and LS composition is very similar with those of DP, SP, WP, SC and DC composition described above respectively.Composition for the treatment of seed can comprise a kind of for assisting said composition to be attached to reagent (such as a kind of mineral oil or a kind of film forming restraining mass) on this seed.
Composition of the present invention can comprise one or more additives to improve the biological property of said composition (such as by the wettability on improvement surface, delay or distribution; Rain fastness on treated surface; Or there is the absorption of compound and the mobility of Formula I).These additives comprise tensio-active agent (SFA), oil base spray additives, such as some mineral oil, vegetables oil or crude vegetal (as soybean oil and rapeseed oil), and they and other biological strengthen the blend of adjuvant (can contribute to or change the composition of effect of the compound with Formula I).Can by such as adding ammonium salt with/Huo phosphonium salt, and/or optionally the penetration enhancer of at least one as fatty alcohol alkoxy compound (as rapeseed methylester) or vegetable oil esters class improves effect of the compound with Formula I.
Wetting agent, dispersion agent and emulsifying agent can be cationic, anionic, amphoteric or non-ionic surfactant (SFA).
The cationic SFA be applicable to comprises quaternary ammonium compound (such as cetyl trimethylammonium bromide), tetrahydroglyoxaline and amine salt.
The anionic SFA be applicable to comprises an alkali metal salt of lipid acid, the salt (such as Sulfuric acid,monododecyl ester, sodium salt) of analiphatic sulphur acid monoester, salt (the such as Sodium dodecylbenzene sulfonate of the aromatics of sulfonation, calcium dodecylbenzene sulphonate, the mixture of butyl naphthalene sulfonate and two-sec.-propyl-sodium naphthalene sulfonate and three-sec.-propyl-sodium naphthalene sulfonate), ether sulfate, ether alcohol sulfate (such as laureth-3-sodium sulfate), ether carboxylate (such as laureth-3-carboxylic acid sodium), phosphoric acid ester (from one or more fatty alcohol and phosphoric acid (mainly monoesters) or and Vanadium Pentoxide in FLAKES (mainly diester) between the product that reacts, reaction such as between lauryl alcohol and four phosphoric acid, these products can be ethoxylated in addition), sulfosuccinic acid amides hydrochlorate, paraffin or alkene sulfonate, taurate and ligninsulfonate.
The amphoteric SFA be applicable to comprises trimethyl-glycine, propionic salt and glycinate.
The SFA of this non-ionic type be applicable to comprises alkylene oxides (such as oxyethane, propylene oxide, butylene oxide ring or its mixture) and aliphatic alcohols (such as oleyl alcohol or hexadecanol) or the condensation product with alkylbenzene phenols (such as octyl phenol, nonylphenol or octyl cresol); The partial ester of derivation of self-long chain lipid acid or hexitan; The condensation product of described partial ester and oxyethane; Block polymer (comprising oxyethane and propylene oxide); Alkylolamide; Monoesters (such as fatty acid polyglycol ester); Amine oxide (such as lauryl dimethyl amine oxide); And Yelkin TTS.
The suspension agent be applicable to comprises lyophilic colloid (such as polysaccharide, polyvinylpyrrolidone or Xylo-Mucine) and swelling clay (such as wilkinite or attapulgite).
The compound with Formula I can be used by any means of killing harmful organism compound of using that oneself knows.Such as, it (preparation or do not prepare) can directly be applied to (the habitat of such as these harmful organisms, place, place of these harmful organisms or these harmful organisms, or be subject to the planting plants of pest infection), or be applied to any part of plant, comprise leaf, stem, branch or root, be applied to the seed before plantation, or be applied to plant and growing or by by other media (such as soil in root week of planting, normal soil, the planting system that paddy field water either or water are planted), or it can be sprayed, dusting, used by dipping, use as butterfat or paste preparation, to use as steam or by by composition (such as particulate composition or the composition that wraps in water-soluble bag) distribution or and use in burying or in aqueous environments.
The compound with Formula I can also be injected in plant or with electrodynamic spraying techniques or other low volume methods and be sprayed on plant, or is used by soil or aerial irrigation systems.
Composition as aqueous formulation (aqueous solution or dispersion) provides with the form of the enriched material containing a high proportion of activeconstituents generally, and this enriched material is added to the water before the use.These enriched materials can comprise DC, SC, OD, EC, EW, ME, SG, SP, WP, WG and CS, usually need to be able to take standing storage and after such storage, can add to form aqueous formulation in water, these aqueous formulations keep all combined material continuous time to be enough to be used by conventional spray appliance.This kind of aqueous formulation can comprise the compound (such as, by weight 0.0001% to 10%) with Formula I of variable quantity, and this depends on the object that they use for it.
Have Formula I compound can with fertilizer (such as nitrogenous, containing potassium or phosphorous fertilizer, and more particularly ammonium nitrate and/or urea fertilizer) used in combination.Suitable preparation type comprises fertiliser granulates.These mixtures compatibly comprise by weight up to 25% the compound with Formula I.
Especially, preferred composition (%=weight percent) composed as follows:
emulsifiable concentrate:
Activeconstituents: 1% to 95%, preferably 5% to 20%
Tensio-active agent: 1% to 30%, preferably 10% to 20%
Solvent: 5% to 98%, preferably 70% to 85%
dirt agent:
Activeconstituents: 0.1% to 10%, preferably 0.1% to 1%
Solid carrier: 99.9% to 90%, preferably 99.9% to 99%
suspension-concentrates:
Activeconstituents: 5% to 75%, preferably 10% to 50%
Water: 94% to 24%, preferably 88% to 30%
Tensio-active agent: 1% to 40%, preferably 2% to 30%
wettable powder:
Activeconstituents: 0.5% to 90%, preferably 1% to 80%
Tensio-active agent: 0.5% to 20%, preferably 1% to 15%
Solid carrier: 5% to 99%, preferably 15% to 98%
granule:
Activeconstituents: 0.5% to 30%, preferably 3% to 15%
Solid carrier: 99.5% to 70%, preferably 97% to 85%
prepare example:
" Mpt. " refer in DEG C fusing point.Free radical represents methyl group.
lCMS method:
method (SQD13)
Spectrum is recorded on the mass spectrograph (the mono-quadrupole mass spectrometer of SQD) from Waters, it is equipped with a kind of electrospray source (polarity: positive ion or negative ion, capillary voltage: 3.00kV, taper hole scope: 30-60V, extractor: 2.00V, source temperature: 150 DEG C, desolvation temperature: 350 DEG C, taper hole gas flow: 0L/Hr, desolvation gas flow: 650L/Hr, mass range: 100 to 900Da) and a kind of AcquityUPLC from Waters: binary pump, heating column compartment and diode-array detector.Solvent degasser, binary pump, heating column compartment and diode-array detector.Post: this UPLCHSST3 of water, 1.8
μm, 30x2.1mm, temperature: 60 DEG C, DAD wavelength region (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05%HCOOH, B=acetonitrile+0.05%HCOOH: gradient: gradient: 0min0%B, 100%A; 1.2-1.5min100%B; Flow (ml/min) 0.85
method (ZCQ13):
Mass spectrum is recorded on the mass spectrograph (the mono-quadrupole mass spectrometer of ZQ) from Waters (Waters), it is equipped with a kind of electrospray source (polarity: positive ion or negative ion, capillary voltage: 3.00kV, taper hole scope: 30-60V, extractor: 2.00V, source temperature: 150 DEG C, desolvation temperature: 350 DEG C, taper hole gas flow: 0L/Hr, desolvation gas flow: 650L/Hr, mass range: 100 to 900Da) and a kind of AcquityUPLC from Waters: binary pump, heating column compartment and diode-array detector.Solvent degasser, binary pump, heating column compartment and diode-array detector.Post: this UPLCHSST3 of water, 1.8
μm, 30x2.1mm, temperature: 60 DEG C, DAD wavelength region (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05%HCOOH, B=acetonitrile+0.05%HCOOH: gradient: gradient: 0min0%B, 100%A; 2.7-3.0min100%B; Flow (ml/min) 0.85.
method (ZDQ13):
Mass spectrum is recorded on the mass spectrograph (the mono-quadrupole mass spectrometer of ZQ) from Waters (Waters), it is equipped with a kind of electrospray source (polarity: positive ion or negative ion, capillary voltage: 3.00kV, taper hole scope: 30-60V, extractor: 2.00V, source temperature: 150 DEG C, desolvation temperature: 350 DEG C, taper hole gas flow: 0L/Hr, desolvation gas flow: 650L/Hr, mass range: 100 to 900Da) and a kind of AcquityUPLC from Waters: binary pump, heating column compartment and diode-array detector.Solvent degasser, binary pump, heating column compartment and diode-array detector.Post: this UPLCHSST3 of water, 1.8
μm, 30x2.1mm, temperature: 60 DEG C, DAD wavelength region (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05%HCOOH, B=acetonitrile+0.05%HCOOH: gradient: gradient: 0min0%B, 100%A; 1.2-1.5min100%B; Flow (ml/min) 0.85.
method (ZQ2000):
From the ZQ2000 mass spectrograph (single-phase quadrupole mass spectrometer) of water this (Waters)
Ionization method: electron spray(ES)
Polarity: positive ion
Kapillary (kV) 3.5, taper hole (V) 60.00, extractor (V) 3.00, source temperature (DEG C) 150, desolventizing temperature degree (DEG C) 350, taper hole blowback air-flow (L/Hr) 50, desolventizing air-flow (L/Hr) 800
Mass range: 140 to 800Da
DAD wavelength region (nm): 210 to 400
Method: this ACQUITYUPLC of water using following HPLC gradient condition
(solvent orange 2 A: water/methyl alcohol 9:1,0.1% formic acid, and solvent B: acetonitrile, 0.1% formic acid)
Post type: this (Waters) ACQUITYUPLCHSST3 of water; Column length: 30mm; Column internal diameter: 2.1mm; Particle size: 1.8 microns; Temperature: 60 DEG C.
1h and
19fNMR measures: measure on Brucker400MHz or 300MHz mass spectrograph, provide chemical shift relative to TMS standard with ppm.Measure spectrum in the solution of specifying.
Mass spectrometry method MS
From the LC-20AD mass spectrograph (single quadrupole mass spectrometer) of Shimadzu (Shimadzu)
Instrument parameter:
Ionization method: electron spray(ES)
Polarity: positive ion and negative ion
Kapillary (kV) 1.50
Taper hole (V) is unknown
Extractor (V) 5.00
Source temperature (DEG C) 200
Desolventizing temperature (DEG C) 250
Taper hole blowback air-flow (l/Hr) 90
Desolventizing air-flow (l/Hr) 90
Mass range: 50Da to 1000Da
example P1:2-methyl-7-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-4-(trifluoro
methyl)-2,3-dihydrobenzo thiophene 1,1-dioxide (compd A 1.014-B2.022):
steps A: 2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-4-(three
methyl fluoride)-2,3-dihydrobenzo thiophene-7-methane amides:
By 2-methyl isophthalic acid, 1-dioxo-4-(trifluoromethyl)-2,3-dihydrobenzo thiophene-7-carboxylic acid (308mg, 1.05mmol, as prepared in WO9909023) and N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamines (200mg, 1.05mmol, as prepared in WO2012/092051) suspension 3-(ethylimino methene amido)-N in THF (15ml), N-dimethyl-propyl-1-amine (487mg, 3.14mmol) and pyridine (100mg, 1.26mmol) process.This reaction mixture is stirred 18 hours and then dilutes with ethyl acetate and 1NHCl.Be separated organic phase and aqueous phase is extracted with ethyl acetate.By the organic phase washed with water merged, use anhydrous Na
2sO
4drying, filters and concentrates under vacuo.By flash chromatography (using ethyl acetate: hexanaphthene 1:1 wash-out), provide the title product (105mg, 21%) in white solid.LCMS (method SQD13): 468 (M+H), retention time 0.97min.
step B:2-methyl-7-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-4-(fluoroform
base)-2,3-dihydrobenzo thiophene 1,1-dioxide (compd A 1.014-B2.022):
By 2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-4-(trifluoromethyl)-2,3-dihydrobenzo thiophene-7-methane amide (71mg, 0.15mmol) solution be dissolved in toluene-4-sulfonic acid (8mg, 0.05mmol) in 1-methylpyrrolidin-2-ketone (1ml) heats 100min at 160 DEG C in microwave.At this moment, after, this reaction mixture is poured in water, is extracted with ethyl acetate, use anhydrous Na
2sO
4drying, filters and reduced under vacuum.The product hexanaphthene of acquisition is ground, to provide the title compound (45mg, 66%) of mpt.206 DEG C in white solid.LCMS (method SQD13): 450 (M+H), retention time 0.99min.
1HNMR(400MHz,CDCl
3)□ppm8.77(d,J＝1.5Hz,1H)；8.42(d,J＝1.5Hz,1H)；8.05(d,J＝8.1Hz,1H)；7.75(d,J＝7.1Hz,1H)；3.90(s,3H)；3.74(d,J＝16.9,8.1Hz,1H)3.52-3.68(m,1H)3.19(dd,J＝16.87,8.1Hz,1H)；1.55ppm(d,J＝7.0Hz,3H)。
the bromo-2-methyl of example P2:4--7-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-2,
3-dihydrobenzo thiophene 1,1-dioxide (compd A 1.014-B2.023):
the bromo-2-methyl of steps A: 4--N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-
2,3-dihydrobenzo thiophene-7-methane amide:
At room temperature, by bromo-for 4-2-methyl isophthalic acid, 1-dioxo-2,3-dihydrobenzo thiophene-7-carboxylic acid (320mg, 1mmol, as prepared in WO9909023) solution oxalyl chloride (170mg, 1.3mmol) in methylene dichloride (10ml) and 1-2 drip DMF process.After 1 hour, add N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamines (200mg, 1.0mmol) and triethylamine (100mg, 1.2mmol), and at room temperature stir this reaction mixture until reacted.By this reaction mixture dchloromethane, wash with water, use anhydrous Na
2sO
4drying, filters and concentrates under vacuo.By flash chromatography (using ethyl acetate: hexanaphthene 1:1 wash-out), to provide the title compound (240mg, 48%) in yellow solid.LCMS (method SQD13): 478/480 (M+H), retention time 0.95min.
the bromo-2-methyl of step B:4--7-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-2,3-
dihydrobenzo thiophene 1,1-dioxide (A1.014-B2.023)
By bromo-for 4-2-methyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-1,1-dioxo-2,3-dihydrobenzo thiophene-7-methane amide (210mg, 0.44mmol) solution be dissolved in toluene-4-sulfonic acid (23mg, 0.13mmol) in 1-methylpyrrolidin-2-ketone (3ml) heats 1 hour at 160 DEG C in microwave.At this moment, after, this reaction mixture is poured in water, is extracted with ethyl acetate, use anhydrous Na
2sO
4drying, filters and reduced under vacuum.By flash chromatography (using ethyl acetate: hexanaphthene (0/100)-> (50/50) wash-out), provide the title compound in white crystalline.LCMS (method SQD13): 460/462 (M+H), retention time 0.97min.
1HNMR(400MHz,CDCl
3)□ppm8.76(d,J＝1.10Hz,1H)；8.41(d,J＝1.1Hz,1H)；8.22(d,J＝7.70Hz,1H)；7.73(d,J＝7.70Hz,1H)；4.02(dd,J＝17.8,7.5Hz,1H)；3.44-3.60(m,1H)；3.35(dd,J＝17.8,7.5Hz,1H)；2.74(s,3H)1.51ppm(d,J＝7.0Hz,3H)。
example P3:2-[4-ethylsulfonyl-6-(trifluoromethyl) pyridazine-3-base]-3-methyl-6-(trifluoromethyl) miaow
azoles is [4,5-b] pyridine (A1.014-B1.058) also.
steps A: 5-Ethylsulfanyl-3-(trifluoromethyl)-1H-pyridazine-6-ketone.
EtSNa (100mg, 1.2mmol) is added in the solution of the bromo-3-of 5-(trifluoromethyl)-1H-pyridazine-6-ketone (243mg, 1mmol, as prepared in WO2008128995) in 10mlDMF.After interpolation, by this mixture stirring at room temperature 2 hours.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and under reduced pressure concentrate.This resistates is carried out purifying by silica gel column chromatography, to provide 5-Ethylsulfanyl-3-(trifluoromethyl)-1H-pyridazine-6-ketone (182mg, 81%).
1HNMR(300Mz,DMSO-d
6):δ:1.27(t,3H),3.00(q,2H),7.38(s,1H),13.63(s,1H)；
19FNMR(400MHz,DMSO-d
6):δ-65.49(s,3F)；ESI-MS:223(M-H)
-。
the chloro-4-Ethylsulfanyl of step B:3--6-(trifluoromethyl) pyridazine.
By 5-Ethylsulfanyl-3-(trifluoromethyl)-1H-pyridazine-6-ketone (5.8g, 26mmol) in 25mlPOCl
3in mixture backflow 16h.Then, this reaction mixture is cooled to room temperature, and under reduced pressure distills POCl
3.This resistates to be poured in water and to be adjusted to alkalescence with sodium hydroxide.Gained mixture is extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and under reduced pressure concentrate.By crude product by purification by silica gel column chromatography, to provide the chloro-4-Ethylsulfanyl of 3--6-(trifluoromethyl) pyridazine (4.9g, 79%).
1HNMR(300Mz,DMSO-d
6):δ1.31(t,3H),3.23(q,2H),8.00(s,1H)；
1FNMR(300Mz,DMSO-d
6):δ-65.19(s,3F)；ESI-MS(+):243(M+H)
+。
step C:4-Ethylsulfanyl-6-(trifluoromethyl) pyridazine-3-methyl-formiate.
CO (carbon monoxide converter) gas is introduced the chloro-4-Ethylsulfanyl of 3--6-(trifluoromethyl) pyridazine (2.5g, 10mmol), Pd (OAc)
2(232mg, 0.1mmol), dppf (572mg, 0.1mmol) and Et
3in the mixture of N (3.1g, 30mmol) in 30mlMeOH, and internal pressure is increased to 1.5MPa.Then, this reaction is stirred 16h at 80 DEG C.This reaction mixture be cooled to room temperature and under reduced pressure concentrate.This resistates is carried out purifying by silica gel column chromatography, to provide 4-Ethylsulfanyl-6-(trifluoromethyl) pyridazine-3-methyl-formiate (1.0g, 37%).
1HNMR(300Mz,DMSO-d
6):δ1.28(t,3H),3.19(q,2H),3.99(s,3H),8.01(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-65.61(s,3F)；ESI-MS(+):267(M+H)
+,289(M+Na)
+。
step D:4-Ethylsulfanyl-6-(trifluoromethyl) Pyridazine 3 carboxylic acid.
By 4-Ethylsulfanyl-6-(trifluoromethyl) pyridazine-3-methyl-formiate (532mg, 2mmol) and LiOH (96mg, 4mmol) in 30mlTHF and 6mlH
2mixture in O at room temperature stirs 30min.Then this mixture is poured in water, and pH dilute hydrochloric acid is adjusted to 3-4.Gained mixture is extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and under reduced pressure concentrate, to obtain 4-Ethylsulfanyl-6-(trifluoromethyl) Pyridazine 3 carboxylic acid (398mg, 79%).
1HNMR(300Mz,DMSO-d
6):δ1.22(t,3H),3.16(q,2H),8.03(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-65.52(s,3F)；ESI-MS(-):267(M-H)
-。
step e: 4-Ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-6-(fluoroform
base) pyridazine-3-methane amide.
By 4-Ethylsulfanyl-6-(trifluoromethyl) Pyridazine 3 carboxylic acid (230mg, 0.9mmol), N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamines (209mg, 1.1mmol, as prepared in WO2012092051), HATU (520mg, 1.4mmol), the mixture of DIPEA (235mg, 1.8mmol) in 20mlDMF at room temperature stirs 16h.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.This resistates is carried out purifying by silica gel column chromatography, to provide 4-Ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-6-(trifluoromethyl) pyridazine-3-methane amide (369mg, 95%).
1HNMR(300Mz,DMSO-d
6):δ1.30(t,3H),2.87(d,3H),3.12(q,2H),7.03(s,1H),7.77(s,1H),8.07(s,1H),8.33(s,1H),10.54(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ:-65.43(s,3F),-58.81(s,3F)；ESI-MS(+):426(M+H)
+。
step D:2-[4-Ethylsulfanyl-6-(trifluoromethyl) pyridazine-3-base]-3-methyl-6-(trifluoromethyl) imidazoles
and [4,5-b] pyridine (compd A 1.014-B1.050):
4-Ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-6-(trifluoromethyl) pyridazine-3-methane amide (369mg, 0.9mmol) in 10mlAcOH is refluxed 2 hours.Then this reaction mixture is concentrated under vacuo.By this resistates by silica gel flash column chromatography, to provide 2-[4-Ethylsulfanyl-6-(trifluoromethyl) pyridazine-3-base]-3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine (compd A 1.014-B1.050,181mg, 51%).
1HNMR(300Mz,DMSO-d
6):δ1.27(t,3H),3.20(q,2H),4.07(s,1H),8.12(s,1H).8.75(s,1H),8.93(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-66.44(s,3F),-58.33(s,3F)；ESI-MS(+):408(M+H)
+.)
+。Mpt.149℃-156℃。LCMS(SQD13)Rt.1.12min，408(M+H)。
step e: 2-[4-ethylsulfonyl-6-(trifluoromethyl) pyridazine-3-base]-3-methyl-6-(trifluoromethyl) imidazoles
and [4,5-b] pyridine (A1.014-B1.058):
By 2-[4-Ethylsulfanyl-6-(trifluoromethyl) pyridazine-3-base]-3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine (109mg, 0.3mmol) and m-CPBA (232mg, 1.3mmol) in 20mlCH
2cl
2in mixture at room temperature stir 2h.Then by this mixture saturated sodium sulfite, aqueous sodium bicarbonate washing, and dried over sodium sulfate is used.After filtration, this solvent is under reduced pressure concentrated.By this resistates by silica gel flash chromatography, to obtain title compound (compd A 1.014-B1.058) (113mg, 96%).
1HNMR(300Mz,DMSO-d
6):δ1.26(t,3H),3.91(s,3H),3.94(q,2H),8.77(s,1H),8.79(s,1H),8.97(s,1H)；
19F-NMR(300Mz,DMSO-d
6):δ-65.30(s,3F),-58.32(s,3F)；ESI-MS(+):440(M+H)
+.)Mpt.172℃-174℃。LCMS(ZCQ13)Rt.1.06min，440(M+H)。
example P4:5-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base] thiophene
azoles (V13.05):
steps A 5-Ethylsulfanyl 4-thiazolecarboxylic acid ethyl ester:
At-40 DEG C, the dropwise of isocyanide ethyl acetate (5.6g, 0.05mol) in 100mlTHF is added in the suspension of potassium tert.-butoxide (6.1g, 0.055mol) in 20mlTHF.After the addition, this mixture is cooled to-60 DEG C, while remaining on below-50 DEG C by temperature, dropwise adds dithiocarbonic anhydride (3.8g, 0.05mol).Then, this mixture heated to 10 DEG C and add monobromethane (5.4g, 0.05mol).This mixture stirred in addition 2h and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to obtain compound 5-Ethylsulfanyl 4-thiazolecarboxylic acid ethyl ester (5.6g, 52%).
1HNMR(300MHz,DMSO-d
6):δ1.27-1.37(m,6H),3.03(q,2H),4.25(q,2H),8.97(s,1H)；ESI-MS(+):218(M+H)
+,240(M+Na)
+。
step B:5-Ethylsulfanyl thiazole-4-carboxylic acid.
By 5-Ethylsulfanyl 4-thiazolecarboxylic acid ethyl ester (4.6g, 0.02mol) and NaOH (1.68mg, 0.04mol), the mixture in 25ml water and 50mlTHF at room temperature stirs and spends the night.Then, this reaction mixture is poured in dilute hydrochloric acid.Then, the throw out piled up is filtered, washes with water, drying under reduced pressure, to obtain title compound (3.9g, 90%).
1HNMR(300MHz,DMSO-d
6):δ1.32(t,3H),3.00(q,2H),8.94(s,1H),12.94(brs,1H)；ESI-MS(+):190(M+H)
+,212(M+Na)
+；HPLC：99.9％。
step C:N-[4-amino-6-(trifluoromethyl)-3-pyridyl] t-butyl carbamate:
To 6-(trifluoromethyl) pyridine-3,4-diamines (3.14g, 17.73mmol, as prepared in U.S.7767687) add tertbutyloxycarbonyl tert-butyl carbonate (4.64g in solution in THF (50ml), 21.27mmol), and this mixture is stirred at 50 DEG C.After 8 hours, add 1.1g (5.0mmol) tertbutyloxycarbonyl tert-butyl carbonate in addition, and continue to stir 4 hours again at 50 DEG C.Then this reaction mixture is concentrated under vacuo, and brown residue is suspended in methylene dichloride, filter and drying under vacuo, to provide the title compound in white crystalline.LCMS (method SQD13): retention time 0.79min, 278 (M+H).
step D:N-[4-amino-6-(trifluoromethyl)-3-the pyridyl]-N-Methyl-carbamic acid tert-butyl ester
At 20 DEG C-25 DEG C, through a time period of 20min, to sodium hydride (0.648g, N-[4-amino-6-(the trifluoromethyl)-3-pyridyl] t-butyl carbamate (3.92g, 14.14mmol) be dissolved in 20mlDMF is dropwise added in stirred suspension 14.85mmol) in 30mlDMF.After at room temperature stirring 15min, add methyl iodide (2.21g, 15.55mmol).At ambient temperature after 30min, this mixture is poured onto 200ml waterborne, is extracted with ethyl acetate twice, and by the organic constituent priority water of merging and salt water washing, use Na
2sO
4drying also concentrates under vacuo.Recrystallization crude product from ethyl acetate/heptane, to provide the title compound (3.18g) in white crystalline.LCMS (method SQD13): retention time 0.85min, 292 (M+H).
step e: N3-methyl-6-(trifluoromethyl) pyridine-3,4-diamines:
To N-[4-amino-6-(trifluoromethyl)-3-the pyridyl]-N-Methyl-carbamic acid tert-butyl ester (3.53g, hydrogenchloride (the 2M solution of 18ml in water is added in limpid colourless solution 12.119mmol) in Yu diox, 36.36mmol), and by this mixture backflow is heated to.After air release stops, this reaction mixture is cooled to room temperature, and processes with solid sodium bicarbonate (3.1g, 36.9mmol).This slurry dilute with water is extracted with ethyl acetate twice.By the organic layer priority water of merging and salt water washing, use Na
2sO
4drying also concentrates, under vacuo to provide the title compound that 2.25g is clear crystal shape, Mpt, 138 DEG C-140 DEG C; LCMS (method SQD13):, residence time 0.24min, 192 (M+H).
Alternately,
n3-methyl-6-(trifluoromethyl) pyridine-3,4-diaminesobtain by following program:
Methyl iodide (0.8mL) is added in solution in acetonitrile (10mL) to 6-(trifluoromethyl) pyridine-3,4-diamines (2.0g, 12.2mmol) and salt of wormwood (3.2g, 23.1mmol).This reaction mixture is spent the night 30 DEG C of stirrings.Filter out salt of wormwood; Filtrate is dry also with purification by silica gel column chromatography (oil: EtOAc=4:3) under vacuo, to obtain title compound (0.32g, the productive rate: 37%) in faint yellow solid shape.
1HNMR(400MHz,DMSO-d
6):δ(ppm)7.57(s,1H),6.83(s,1H),5.82(s,2H),5.23(d,J＝4.8Hz,1H),2.80(d,J＝4.8Hz,3H)。
19FNMR(300MHz,DMSO-d6):δ(ppm)-60.12(s,3F)。ESI-MS(+):192(M+H)。
step F: 5-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base] thiazole
(compd A 6.002-B7.037):
By 5-Ethylsulfanyl thiazole-4-carboxylic acid (567mg, 3mmol), N3-methyl-6-(trifluoromethyl) pyridine-3,4-diamines (483mg, mixture backflow 16h 3mmol) with N-(3-dimethylaminopropyl)-N '-ethylcarbodimide hydrochloride (EDC.HCL) (576mg, 3.6mmol) in 20ml pyridine.This reaction mixture reduced under vacuum is passed through purification by silica gel column chromatography, to provide title compound (120mg), 5-Ethylsulfanyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl] thiazole-4-carboxamide (51mg) and N-[4-amino-6-(trifluoromethyl)-3-pyridyl]-5-Ethylsulfanyl-N-methYl-thiazol-4-methane amide (162mg).By latter two compound dissolution in 10mlAcOH and the 16h that refluxes.Then this mixture is concentrated under vacuo, and by this resistates by purification by silica gel column chromatography, to provide other title compound (140mg).
1HNMR(400MHz,DMSO-d
6):δ1.34(t,3H),3.08(q,2H),4.23(s,3H),8.20(s,1H),9.17(s,1H),9.27(s,1H)；
19F-NMR(400MHz,DMSO-d
6):δ-59.68(s,3F)；ESI-MS：345(M+H)
+,367(M+Na)
+；Mpt.167℃-169℃。
step G:5-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base] thiazole (v13.05
)
By 5-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4 in 10ml methylene dichloride, 5-c] pyridine-2-base] thiazole (140mg, 0.4mmol) at room temperature stir 0.5h with m-CPBA (280mg, 1.6mmol).Then this mixture is poured into Na
2cO
3and Na
2sO
3in the saturated solution of Yu Shuizhong, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (147mg, 96%).
1hNMR (400MHz, DMSO-d
6): δ 1.28 (t, 3H), 4.04 (q, 2H), 4.05 (s, 3H), 8.32 (s, 1H), 9.29 (s, 1H), 9.70 (s, 1H);
19f-NMR (400MHz, DMSO-d
6): δ-58.84 (s, 3F); ESI-MS (+): 377 (M+H)
+, 399 (M+Na)
+; LCMS (method SQD13) Rt.0.85min377 (M+H).Mpt.178℃-179℃
example P5:2-[5-(difluoro-methoxy)-3-ethylsulfonyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)
imidazo [4,5-c] pyridine (compound V12.19):
the chloro-5-of steps A: 2,3-bis-[(4-p-methoxy-phenyl) methoxyl group] pyridine
By 5,6-dichloropyridine-3-alcohol (8.2g, 50mmol), 4-methoxy-benzyl chlorine (11.8g, 75mmol) and K
2cO
3(21.0g, 150mmol) is in CH
3mixture backflow 6h in CN (250ml).Then, this mixture be cooled to room temperature and filter.Filtrate is under reduced pressure concentrated and this resistates is passed through purification by silica gel column chromatography, to provide the title compound (10.0g, 70% productive rate) in white solid.
1HNMR(400MHz,DMSO-d
6):δ3.72(s,3H),5.09(s,2H),6.92(d,J＝8.8Hz,2H),7.35(d,J＝8.8Hz,2H),7.89(d,J＝2.8Hz,1H),8.15(d,J＝2.8Hz,1H)；ESI-MS(+):284(M+H)
+；Mpt.:124℃-125℃。
the chloro-5-of step B:3-[(4-p-methoxy-phenyl) methoxyl group] pyridine-2-ethyl formate
CO gas is introduced 2,3-bis-chloro-5-[(4-p-methoxy-phenyl) methoxyl group] pyridine (10.0g, 35.2mmol), dppf (975mg, 1.8mmol), Pd (OAc)
2(158mg, 0.7mmol) and Et
3in the mixture of N (10.2ml, 70.4mmol) in 110mlEtOH, and internal pressure is increased to 1.6MPa.By this reaction mixture 125 DEG C of stir abouts 7 hours.Then, this mixture be cooled to room temperature and filter.Filtrate is under reduced pressure concentrated and this resistates is passed through purification by silica gel column chromatography, to obtain the title compound (6.8g, 60% productive rate) in faint yellow solid shape.
1HNMR(400MHz,DMSO-d
6):δ1.26(t,J＝6.8Hz,3H),3.72(s,3H),4.28(q,J＝6.8Hz,2H),5.15(s,2H),6.92(d,J＝8.0Hz,2H),7.37(d,J＝8.0Hz,2H),7.76(d,J＝2.0Hz,1H),8.32(d,J＝2.0Hz,1H)；ESI-MS(+):322(M+H)
+,345(M+Na)
+；Mp:45℃-46℃。
step C:3-Ethylsulfanyl-5-[(4-p-methoxy-phenyl) methoxyl group] pyridine-2-ethyl formate
Chloro-for 3-5-[(4-p-methoxy-phenyl) methoxyl group] pyridine-2-ethyl formate (6.4g, 0.02mol) and the mixture of EtSNa (3.35g, 0.04mol) in 50mlDMF are stirred 4h at 90 DEG C.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and under reduced pressure concentrate.By this resistates by purification by silica gel column chromatography, to provide title compound (3g, 43% productive rate).
1HNMR(400MHz,DMSO-d
6):δ1.22(t,3H),1.29(t,3H),2.97(q,2H),3.76(s,3H),4.27(q,2H),5.24(s,2H),6.96(d,2H),7.34(d,1H),7.41(d,2H),8.15(d,1H)；ESI-MS(+):370(M+Na)
+。
step D:3-Ethylsulfanyl-5-[(4-p-methoxy-phenyl) methoxyl group] pyridine-2-carboxylic acids:
By ethyl-3-Ethylsulfanyl-5-[(4-p-methoxy-phenyl) methoxyl group] pyridine-2-manthanoate (3g, 0.009mol) and the mixture of NaOH (692mg, 0.017mol) in 10ml water and 30mlTHF at room temperature stir and spend the night.Then, this reaction mixture is poured in dilute hydrochloric acid, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by silica gel flash column chromatography, to provide title compound (2.3g, 83% productive rate).
1HNMR(400MHz,DMSO-d
6):δ1.23(t,3H),2.94(q,2H),3.76(s,3H),5.24(s,2H),6.96(d,2H),7.32(d,1H),7.41(d,2H),8.13(d,1H),12.69(brs,1H)；ESI-MS(+):320(M+H)
+,342(M+Na)
+。
step e: 3-Ethylsulfanyl-5-[(4-p-methoxy-phenyl) methoxyl group]-N-[5-(methylamino)-2-(fluoroform
base)-4-pyridyl] pyridine-2-carboxamide:
By compound 3-Ethylsulfanyl-5-[(4-p-methoxy-phenyl) methoxyl group] pyridine-2-carboxylic acids (284mg, 0.89mmol), N3-methyl-6-(trifluoromethyl) pyridine-3,4-diamines (149mg, 0.89mmol, as prepared in example P4 step e) and the mixture backflow 16h of EDC.HCl (188mg, 0.98mmol) in 10ml pyridine.Then, concentrated under vacuo by this mixture, dilute with water is also extracted with ethyl acetate.By the organic layer Na of merging
2sO
4drying, under reduced pressure concentrates, and to provide thick title product (320mg), it is directly used in next step without being further purified.
step F: 5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base] pyridine-
3-alcohol:
Reflux 3-Ethylsulfanyl-5-[(4-p-methoxy-phenyl) methoxyl group]-N-[5-(methylamino)-2-(the trifluoromethyl)-4-pyridyl] pyridine-2-carboxamide (320mg) in 10mlAcOH 16h.Then this mixture is concentrated under vacuo, and by this resistates by purification by silica gel column chromatography, to provide title compound (151mg).
1H-NMR(400MHz,DMSO-d
6):δ1.18(t,3H),2.91(q,2H),3.96(s,3H),7.34(d,1H),8.11(d,1H),8.22(s,1H),9.18(s,1H),10.74(s,1H)；
19F-NMR(400MHz,DMSO-d
6):δ-64.84(s,3F)；ESI-MS(+):355(M+H)
+。
step G:2-[5-(difluoro-methoxy)-3-Ethylsulfanyl-2-pyridyl]-3-methyl-6-(trifluoromethyl) miaow
azoles is [4,5-c] pyridine also:
At 50 DEG C, by CHClF
2gas introduces 5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base] pyridine-3-alcohol (100mg, 0.28mmol) and Cs
2cO
32 hours are continued in (460mg, 1.41mmol) mixture in 10mlDMF.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title product (94mg, 82%).
1HNMR(400MHz,DMSO-d
6):δ1.35(t,3H),2.93(q,2H),4.07(s,3H),6.67(t,1H),7.52(d,1H),8.19(s,1H),8.36(d,1H),8.95(s,1H)；
19F-NMR(400MHz,DMSO-d
6):δ-81.81(d,1F),-66.25(s,3F)；ESI-MS(+):405(M+H)
+,427(M+Na)
+,459(M+MeOH+Na)
+；HPLC:98.2％
step H:2-[5-(difluoro-methoxy)-3-ethylsulfonyl-2-pyridyl]-3-methyl-6-(trifluoromethyl) miaow
azoles is [4,5-c] pyridine (compound V12.19) also:
By 2-[5-(difluoro-methoxy)-3-Ethylsulfanyl-2-pyridyl]-3-methyl-6-(trifluoromethyl) imidazo [4 in 5ml methylene dichloride, 5-c] pyridine (80mg, 0.2mmol) at room temperature stir 0.5h with m-CPBA (136mg, 0.8mmol).Then this mixture is poured into Na
2cO
3and Na
2sO
3saturated aqueous solution in, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (67mg, 88%).
1HNMR(400MHz,DMSO-d
6):δ1.19(m,3H),3.78(d,3H),3.90(s,3H),6.77(t,1H),8.11(s,2H),8.30(d,1H),8.86(d,1H),9.00(s,1H)；
19F-NMR(400MHz,DMSO-d
6):δ-78.62(d,1F),-62.07(s,3F)；ESI-MS(+):437(M+H)
+。Mpt.146 DEG C-148 DEG C; LCMS (method SQD13): retention time 1.03 minutes, 405 (M+H).
example P6:6-(2-ethanesulfonyl-6-trifluoromethylpyridin-3-base)-3-Methyl-2-trifluoromethyl-3,5-
dihydro-diimidazole also [4,5-b; 4 ', 5 '-e] pyridine (compound V26.03):
steps A: 3-methyl-6-nitro-2-(trifluoromethyl) imidazo [4,5-b] pyridine:
At 70 DEG C, N2-methyl-5-nitro-pyridine-2,3-diamines (10g, 59.52mmol) in TFA (10mL) is stirred 16h.By this mixture by silicon chromatography purification, to obtain the pure title compound (9.81g, 67%) in yellow solid.
1HNMR(300MHz,d6-DMSO):δ9.46(d,J＝2.4Hz,1H),9.22(d,J＝2.4Hz,1H),4.04(s,3H)。
step B:3-methyl-6-nitro-4-is oxidized-2-(trifluoromethyl) imidazo [4,5-b] pyridine-4-:
To 3-methyl-6-nitro-2-(trifluoromethyl) imidazo [4,5-b] pyridine (5.3g, perhydrit (UHP is added in solution 21.54mmol) in methylene dichloride methylene dichloride (60mL), 6.17g, 65.7mmol), be cooled with an ice bath, and dropwise add TFAA (13.6g, 65.7mmol).This mixture is stirred 18 hours at ambient temperature.TCL display consumes the parent material of about 50%.At DEG C interpolation another batch of UHP (6.08g, 64.63mmol) and a TFAA (13.8g, 64.63mmol).This mixture is stirred 24 hours again in envrionment temperature.By this reaction mixture dilute with water, stir and continue 20min.Be separated organic phase, and by aqueous phase with dichloromethane extraction (3 times).By the organic phase washed with water of merging and salt water washing, use Na
2sO
4drying, and concentrate under vacuo.By this resistates by silicon chromatography purification, to provide the title compound (1.91g) in white solid.
1HNMR(300MHz,d6-DMSO):δ9.17(d,J＝1.8Hz,1H),8.83(d,J＝1.8Hz,1H),4.41(d,J＝1.2Hz,3H)。
the chloro-3-methyl of step C:5--6-nitro-2-(trifluoromethyl) imidazo [4,5-b] pyridine:
3-methyl-6-nitro-4-is oxidized-2-(trifluoromethyl) imidazo [4,5-b] pyridine-4-(2.8g, 10.69mmol) and is dissolved in POCl
3(50mL) in, and return stirring 2 hours.This mixture is poured in frozen water, with EtOAc extraction (3 times).By organic phase NaHCO
3(water-based) and water washing, use Na
2sO
4drying, is evaporated to drying, to obtain thick title compound (3.8g), by it without being further purified for next step.
step D:N5,3-dimethyl-6-nitro-2-(trifluoromethyl) imidazo [4,5-b] pyridin-5-amine:
MeNH is added in the solution of the chloro-3-methyl of compound 5--6-nitro-2-(trifluoromethyl) imidazo [4,5-b] pyridine (3.8g) in ethanol (40mL)
2(water-based, 5mL).This reaction mixture is stirred 18 hours at ambient temperature.This mixture is filtered, and dry under vacuo, to obtain the pure title compound (2.3g) in white solid.
1HNMR(300MHz,d6-DMSO):δ8.90(s,1H),8.64-8.62(m,1H),3.79(d,J＝1.2Hz,3H),3.07(d,J＝4.8Hz,3H)。
step e: N5,3-dimethyl-2-(trifluoromethyl) imidazo [4,5-b] pyridine-5,6-diamines:
At N
2under, to compound N 5,200mg palladium carbon is added in the solution of 3-dimethyl-6-nitro-2-(trifluoromethyl) imidazo [4,5-b] pyridin-5-amine (2.3g, 8.36mmol) in EtOAc (30mL) and methyl alcohol (30mL).At room temperature, use hydrogen balloon by this mixture hydrogenation 4h.By this mixture by diatomite filtration, and filtrate is evaporated to drying.By this resistates by silicon chromatography purification, to provide the title compound (1.6g, 78%) in violet solid shape.
1HNMR(300MHz,d6-DMSO):δ7.01(s,1H),6.29(d,J＝3.3Hz,1H),4.69(s,2H),3.77(d,J＝1.2Hz,3H),2.92(d,J＝4.5Hz,3H)。
the chloro-6-of the bromo-2-of step F: 3-(trifluoromethyl) pyridine:
By chloro-for compound 2-6-(trifluoromethyl) pyridine-3-amine
(5.88g, 30mmol, as prepared in WO2009110475), Isopentyl nitrite (7.02g, 60mmol), p-TsOH (6.19g, 36mmol), TBAB (19.32g, 60mmol) and CuBr
2(1.40g, 6mmol) mixture in 60mlMeCN at room temperature stirs 4h.Then, this mixture is concentrated under vacuo and this resistates is passed through purification by silica gel column chromatography, to provide title compound (5.85g, 75%).
1H-NMR(300Mz,DMSO-d
6):δ7.85(d,1H),8.52(s,1H)；
19F-NMR(300Mz,DMSO-d
6):δ-65.72(s,3F)。
the bromo-2-Ethylsulfanyl of step G:3--6-(trifluoromethyl) pyridine:
By bromo-for 3-2-chloro-6-(trifluoromethyl) pyridine (5.98g, 23mmol) and EtSNa (1.93g, 23mmol), the mixture in 50mlMeCN stirs 2h.Then, this mixture is poured in dilute hydrochloric acid, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (4.06g, 58%).
1H-NMR(300Mz,DMSO-d
6):δ1.26(t,3H),3.08(q,2H),7.50(d,1H),8.20(d,1H)；
19F-NMR(300Mz,DMSO-d
6):δ-65.45(s,3F)。
step H:2-Ethylsulfanyl-6-(trifluoromethyl) Nicotinicum Acidum ethyl ester:
CO (carbon monoxide converter) gas is introduced the bromo-2-Ethylsulfanyl of 3--6-(trifluoromethyl) pyridine (572mg, 2mmol), Pd (OAc)
2(90mg, 0.4mmol), dppf (444mg, 0.8mmol) and Et
3in the mixture of N (1.01g, 10mmol) in 10mlEtOH and 10mlDMF, and internal pressure is increased to 2.7MPa.This mixture is heated 6h at 90 DEG C and is cooled to room temperature.Then, to be poured in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by flash silica chromatography, to provide title compound (795mg, 88%).
1H-NMR(300Mz,DMSO-d
6):δ1.23(t,3H),1.28(t,3H),3.05(q,2H),4.29(q,2H),7.66(d,1H),8.39(d,1H)；
19F-NMR(300Mz,DMSO-d
6):δ-62.88(s,3F)。
step I:2-Ethylsulfanyl-6-(trifluoromethyl) pyridine-3-carboxylic acid:
By 2-Ethylsulfanyl-6-(trifluoromethyl) Nicotinicum Acidum ethyl ester (480mg, 1.7mmol) and KOH (482mg, 8.6mmol), the mixture in 10ml water and 10mlTHF at room temperature stirs 16h.This reaction mixture to be poured in dilute hydrochloric acid and to be extracted with ethyl acetate.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (430mg, 90%).
1H-NMR(300Mz,DMSO-d
6):δ1.23(t,3H),3.02(q,2H),7.64(d,1H),8.37(d,1H),13.85(brs,1H)；
19F-NMR(300Mz,DMSO-d
6):δ-62.78(s,3F)；ESI-MS(-):250(M-H)
-。
step J:2-Ethylsulfanyl-N-[3-methyl-5-(methylamino)-2-(trifluoromethyl) imidazo [4,5-b] pyrrole
pyridine-6-base]-6-(trifluoromethyl) pyridine-3-carboxamide:
By 2-Ethylsulfanyl-6-(trifluoromethyl) pyridine-3-carboxylic acid (251mg, 1mmol), N5,3-dimethyl-2-(trifluoromethyl) imidazo [4,5-b] pyridine-5,6-diamines (245mg, 1.0mmol, the product from the step e in this example), HATU (570mg, mixture 1.5mmol) with DIPEA (258mg, 2mmol) in 10mlDMF stirs 16h.This mixture is concentrated under vacuo, and by purification by silica gel column chromatography, to provide title compound (408mg, 84%).
1HNMR(300Mz,DMSO-d
6):δ1.26(t,3H),2.91(d,3H),3.07(q,2H),3.83(s,3H),6.69(q,1H),7.76(d,1H),7.80(s,1H),8.44(d,1H),9.97(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-62.50(s,3F),-57.02(s,3F)。
step K: 6-(2-Ethylsulfanyl-6-trifluoromethylpyridin-3-base)-3-Methyl-2-trifluoromethyl-3,5-bis-
hydrogen-diimidazole also [4,5-; 4 ', 5 '-e] pyridine:
By 2-Ethylsulfanyl-N-[3-methyl-5-(methylamino)-2-(trifluoromethyl) imidazo [4,5-b] pyridine-6-base]-6-(trifluoromethyl) pyridine-3-carboxamide (382mg, mixture backflow 2h 0.8mmol) in 10mlAcOH, then this mixture is concentrated under vacuo and this resistates is passed through purification by silica gel column chromatography, to provide title compound (231mg, 63%).
1H-NMR(300Mz,CDCl
3):δ1.33(t,3H),3.22(q,2H),3.85(s,3H),4.09(s,3H),7.51(d,1H),7.86(d,1H),8.59(d,1H)；
19FNMR(300Mz,CDCl
3):δ-68.64(s,3F),-63.72(s,3F)；ESI-MS(+):461(M+H)
+,483(M+Na)
+。Mpt.154 DEG C-156 DEG C; LCMS; Retention time 1.13 minutes, 461 (M+H)
step L:6-(2-ethanesulfonyl-6-trifluoromethylpyridin-3-base)-3-Methyl-2-trifluoromethyl-3,5-bis-
hydrogen-diimidazole also [4,5-b; 4', 5'-e] pyridine (compound V26.03):
By 6-(2-Ethylsulfanyl-6-trifluoromethylpyridin-3-base)-3-Methyl-2-trifluoromethyl-3,5-dihydros-diimidazole also [4,5-; 4 ', 5 '-e] pyridine (161mg, 0.35mmol) and the mixture of m-CPBA (242mg, 1.4mmol) in 10ml methylene dichloride at room temperature stir 2h.Then this mixture is poured into NaHCO
3and Na
2sO
3in the saturated solution of Yu Shuizhong, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide the title compound (163mg, 94%) in white solid.
1HNMR(300Mz,CDCl
3):δ1.30(t,3H),3.53(q,2H),3.85(s,3H),4.09(s,3H),8.08(d,1H),8.30(d,1H),8.54(s,1H)；
19FNMR(300Mz,CDCl
3):δ-63.78(s,3F),-59.57(s,3F)；ESI-MS:493(M+H)
+,515(M+Na)
+。Mpt.197 DEG C-199 DEG C; LCMS (method SQD13): retention time 0.95 minute, 493 (M+H).
example P7:4-ethylsulfonyl-5-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base]-2-
(trifluoromethyl) thiazole (compound V14.05):
the bromo-2-of steps A: 4-(trifluoromethyl) thiazole:
By 2,4-bis-bromo thiazole (24.3g, 0.1mol), FSO
2cF
2cOOCH
3(23.0g, 0.12mmol) and the mixture of CuI (19.0g, 0.1mol) in 200mlDMF were 100 DEG C of heating 4 hours.Then, this reaction mixture is poured in water, and under water-aspirator pressure, distill this title compound (22.9g, 83%).By this product without being further purified for next step.
the bromo-2-of step B:4-(trifluoromethyl) thiazole-5-carboxylic acid:
At 60 DEG C, under nitrogen atmosphere, n-BuLi (2.5M in hexane, 62mmol) is slowly added to i-Pr in the anhydrous THF of 150ml
2in NH (6g, 59mmol).After the addition, this mixture is stirred 0.5 hour at the same temperature again.Then, in above mixture, slowly add 4-bromo-2-(trifluoromethyl) thiazole (12g, 52.0mmol), and continue to stir 20min.This mixture is poured in dry ice, and stirs one hour again.Allow this reaction mixture to be warming up to envrionment temperature, with diluted ethyl acetate, and by organic phase priority water and saturated brine washing, by dried over sodium sulfate, filter and drying under vacuo, to provide title product (10.1g, 71%).
the bromo-2-of step C:4-(trifluoromethyl) thiazole-5-carbonyl chloride:
By bromo-for 4-2-(trifluoromethyl) thiazole-5-carboxylic acid (276mg, 1mmol) in 10mlSOCl
2in mixture reflux 4 hours.Distill excessive SOCl
2, to provide thick title product (295mg), it is directly used in next step without being further purified.
the bromo-5-of step D:4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base]-2-(trifluoromethyl)
thiazole:
By bromo-for 4-2-(trifluoromethyl) thiazole-5-carbonyl chloride (477mg, 1.7mmol) with N3-methyl-6-(trifluoromethyl) pyridine-3,4-diamines (330mg, 1.7mmol, as prepared in example P4 step e) mixture in 10ml toluene backflow 16h.Then this reaction mixture is concentrated under vacuo, and by this resistates by purification by silica gel column chromatography, to provide title compound (358mg, 44%).
1HNMR(300Mz,DMSO-d
6):δ:3.98(s,3H),8.30(s,1H),9.28(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-61.58(s,3F),-57.88(s,3F)；ESI-MS:433(M+H)
+。
step e: 4-Ethylsulfanyl-5-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base]-2-
(trifluoromethyl) thiazole:
By EtSNa (123mg, 1.5mmol) add the bromo-5-of 4-[3-methyl-6-(trifluoromethyl) imidazo [4 to, 5-c] pyridine-2-base] in the mixture of-2-(trifluoromethyl) thiazole (315mg, 0.7mmol) in 10mlDMF.After interpolation, by this mixture stirring at room temperature 2 hours.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and under reduced pressure concentrate.By crude product by purification by silica gel column chromatography, to provide title compound (176mg, 58%).
1HNMR(300Mz,DMSO-d
6):δ1.25(t,3H),3.18(q,2H),4.02(s,3H),8.25(s,1H),9.24(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-59.80(s,3F),-55.95(s,3F)；ESI-MS:413(M+H)
+。LCMS (method SQD13): Rt.1.12 minute, 413 (M+H) Mpt.92 DEG C-94 DEG C
step F: 4-ethylsulfonyl-5-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base]-2-
(trifluoromethyl) thiazole (compound V14.05):
By 4-Ethylsulfanyl-5-[3-methyl-6-(trifluoromethyl) imidazo [4,5-c] pyridine-2-base]-2-(trifluoromethyl) thiazole (109mg, 0.3mmol) and m-CPBA (228mg, 1.3mmol) in 15mlCH
2cl
2in mixture at stirring at room temperature 2h.By this reaction mixture saturated sodium sulfite and aqueous sodium bicarbonate dilution, and be separated organic layer, by dried over sodium sulfate, filter and concentrate under vacuo.By this resistates by flash silica chromatography, to provide title compound (71mg, 61%).
1HNMR(300Mz,DMSO-d
6):δ1.16(t,3H),3.51(q,2H),3.89(s,3H),8.28(s,1H),9.27(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-59.81(s,3F),-55.74(s,3F)；ESI-MS:445(M+H)
+,467(M+Na)
+,499(M+MeOH+Na)
+。
example P8:4-ethylsulfonyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl) imidazo [1,2-a] pyridine-2-
base] thiazole (compound V2.11):
the bromo-N-methoxy-. N-methyl of steps A: 4--2-(trifluoromethyl) thiazole-5-methane amide:
By bromo-for 4-2-(trifluoromethyl) thiazole-5-carboxylic acid
(5.8g, 21mmol, as prepared described in example P7 step B), N, O-dimethyl hydroxylamine hydrochloride (2.5g, 25mmol), HATU (9.6g, 25mmol) and the mixture of DIPEA (5.4g, 42mmol) in 35mlDMF at room temperature stir 16h.This mixture to be poured in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (4.7g, 70%).
1HNMR(300Mz,DMSO-d
6):δ3.27(s,3H),3.68(s,3H)；
19FNMR(300Mz,DMSO-d
6):δ-56.33(s,3F)；ESI-MS:341(M+Na)
+。
step B:1-[the bromo-2-of 4-(trifluoromethyl) thiazole-5-base] ethyl ketone:
At 0 DEG C, under nitrogen atmosphere, by MeMgBr, (3M is at middle THF, 15ml, 45mmol) be dropwise added in the solution of the bromo-N-methoxy-. N-methyl of 4--2-(trifluoromethyl) thiazole-5-methane amide (5.7g, 21mmol) in 30ml dry THF.After the addition, this mixture is allowed to heat to envrionment temperature and stir 30min.Then this mixture to be poured in dilute hydrochloric acid and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.This resistates passes through flash silica chromatography, to provide title product (4.8g, 86%).
1HNMR(300Mz,DMSO-d
6):δ2.68(s,3H)；
19FNMR(300Mz,DMSO-d
6):δ-66.14(s,3F)。
the bromo-2-of step C:4-(trifluoromethyl)-5-[7-(trifluoromethyl) imidazo [1,2-a] pyridine-2-base] thiazole:
At 120 DEG C, under air atmosphere, by 1-[the bromo-2-of 4-(trifluoromethyl) thiazole-5-base] ethyl ketone (220mg, 1mmol), 2-amino-4-(trifluoromethyl) pyridine (193mg, 1.2mmol, as prepared in WO2011090122), Cu (OAc)
2.H
2o (12mg, 0.1mmol), 1,10-phenanthrolene (18mg, 0.1mmol), ZnI
2(32mg, 0.1mmol) mixture in 12ml dichlorobenzene stirs 16h.This mixture is concentrated under vacuo, and by this resistates by purification by silica gel column chromatography, to provide title compound (153mg, 36%).
1HNMR(300Mz,DMSO-d
6):δ7.25(d,1H),8.12(s,1H),8.84(d,1H),8.96(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-64.34(s,3F),-62.89(s,3F)；ESI-MS(-):414(M-H)
-；HPLC：97.7％。
step D:4-Ethylsulfanyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl) imidazo [1,2-a] pyridine-2-
base] thiazole:
By EtSNa (157mg, 1.9mmol) be added into the bromo-2-of 4-(trifluoromethyl)-5-[7-(trifluoromethyl) imidazo [1,2-a] pyridine-2-base] in the mixture of thiazole (389mg, 0.9mmol) in 15mlDMF.After the addition, this mixture is stirred 2 hours at ambient temperature.Then this reaction mixture to be poured in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (281mg, 76%).
1HNMR(300Mz,DMSO-d
6):δ1.28(t,3H),3.23(q,2H),7.24(d,1H),8.11(s,1H),8.75(s,1H),8.86(d,1H)；
19FNMR(300Mz,DMSO-d
6):δ-66.81(s,3F),-65.09(s,3F)；ESI-MS(+):398(M+H)
+；HPLC:96.3％。
step e:4-ethylsulfonyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl) imidazo [1,2-a] pyridine-2-base] thiazole
(compound V2.11):
By 4-Ethylsulfanyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl) imidazo [1,2-a] pyridine-2-base] thiazole (80mg, 0.2mmol) and m-CPBA (105mg, 0.6mmol) in 10mlCH
2cl
2in mixture stir 2 hours in envrionment temperature.Then by this mixture saturated sodium sulfite and aqueous sodium bicarbonate washing.Organic layers with sodium sulfate is dry, filter and concentrate under vacuo.By this resistates by flash silica chromatography, to provide title compound (66mg, 77%).
1HNMR(300Mz,DMSO-d
6):δ1.22(t,3H),3.57(q,2H),7.27(d,1H),8.16(s,1H),8.94(d,2H)；
19FNMR(300Mz,DMSO-d
6):δ-48.60(s,3F),-50.52(s,3F)；ESI-MS(+):430(M+H)
+；HPLC:96.9％。Mpt.126℃-128℃
example P9:3-methyl-2-[3-methyl sulphonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) imidazoles
and [4,5-c] pyridine (compound V12.18):
steps A: 3-methyl sulphonyl-5-(trifluoromethyl) pyridine-2-carbonyl chloride:
3-methyl sulphonyl-5-(trifluoromethyl) pyridine-2-carboxylic acids (1.0g, 3.7mmol, as prepared in US20100234603) is suspended in SOCl
2(5mL), in, in this mixture, 1 DMF is added.This reaction mixture is heated to backflow, and stirs 3h.Then under reduced pressure drying is evaporated to, to provide the title compound (1.1g, 100%) in white solid.This resistates is directly used in next step without being further purified.
step B:N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]-3-methyl sulphonyl-5-(fluoroform
base) pyridine-2-carboxamide:
To 3-methyl sulphonyl-5-(trifluoromethyl) pyridine-2-carbonyl chloride (80mg; compound N 3-methyl-6-(trifluoromethyl) pyridine-3 is added in solution 0.3mmol) in 5ml toluene; 4-diamines (60mg; 1.1mmol; as prepared in example P4 step e), then this reaction mixture is heated to 100 DEG C continue 5 hours.After this, be cooled to room temperature and diluted with 15ml water, and being extracted three times with EtOAc.By dry for the organic layers with sodium sulfate merged, and by purification by silica gel column chromatography (EtOAc: sherwood oil=1/4), to provide the title compound (50mg, 40% productive rate) in white solid.
step C:3-methyl-2-[3-methyl sulphonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) imidazoles
and [4,5-c] pyridine (compound V12.18):
5-methyl-N-[2-methyl-5-(methylamino)-4-pyridyl]-3-methyl sulphonyl-pyridine-2-carboxamide (85mg, 0.2mmol) is added into 5ml acetic acid, and is heated by reaction mixture to 100 DEG C of lasting 12h.This reaction mixture be cooled to room temperature and dilute with the water of 20ml, and extracting three times with EtOAc.By dry for the organic layers with sodium sulfate merged, and by purification by silica gel column chromatography (EtOAc: sherwood oil=1/4), to provide the title compound (40mg, 50% productive rate) in white solid.1HNMR(300MHz,CDCl
3)δ3.65(s,3H),3.94(s,3H),8.11(s,1H),8.82(s,1H),9.01(s,1H),9.24(s,1H)。
19FNMR(300Mz,CDCl
3)δ-67.27(s,3H),δ-63.34(s,3H)。ESI-MS:425(M+1)。Mpt..234℃-236℃。LCMS (method SQD13) Rt.0.93 minute, 425 (M+H).
example P10:2-[2-ethylsulfonyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl) imidazo [1,
2-a] pyridine (compound V3.05):
steps A: 2-Ethylsulfanyl-6-(trifluoromethyl) pyridine-3-carbonyl chloride:
By 2-Ethylsulfanyl-6-(trifluoromethyl) pyridine-3-carboxylic acid
(502mg, 2mmol, as prepared in example P6 step I) is in 10mlSOCl
2in mixture reflux 4 hours.Then, excessive SOCl is evaporated
2, to provide title compound (538mg, 100%), it is directly used in next step without being further purified.
step B:2-Ethylsulfanyl-N-methoxy-. N-methyl-6-(trifluoromethyl) pyridine-3-carboxamide:
By crude product 2-Ethylsulfanyl-6-(trifluoromethyl) pyridine-3-carbonyl chloride (538mg, 2mmol), N, O-dimethyl hydroxylamine hydrochloride (588mg, 6mmol) and K
2cO
3(1.66g, 12mmol) mixture in 10mlTHF and 1ml water at room temperature stirs 10min.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.This resistates passes through purification by silica gel column chromatography, to provide title compound (411mg, productive rate: 70%).
1H-NMR(300Mz,DMSO-d
6):δ1.23(t,3H),3.10(q,2H),3.23(s,3H),3.45(s,3H),7.64(d,1H),7.94(d,1H)；
19FNMR(300Mz,DMSO-d
6):δ-62.44(s,3F)。
step C:1-[2-Ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl] ethyl ketone:
At room temperature, to 2-Ethylsulfanyl-N-methoxy-. N-methyl-6-(trifluoromethyl) pyridine-3-carboxamide (411mg, add 1.4mlMeMgBr (3M is in THF) in solution 1.4mmol) in 10mlTHF, and allow this reaction to stir 30min.Then this mixture to be poured onto in water and to be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.This resistates passes through purification by silica gel column chromatography, to provide title compound (290mg, productive rate: 83%).
1H-NMR(300Mz,DMSO-d
6):δ1.22(t,3H),2.60(s,3H),3.02(q,2H),7.71(d,1H),7.52(d,1H)；
19F-NMR(300Mz,DMSO-d
6):δ-67.93(s,3F)。
step D:2-[2-Ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl) imidazo [1,2-
a] pyridine:
By 1-[2-Ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl] ethyl ketone (249mg, 1mmol), 4-(trifluoromethyl) pyridine-2-amine (162mg, 1.2mmol), Cu (OAc)
2h
2o (12mg, 0.1mmol), ZnI2 (32mg, 0.1mmol) and the mixture of 1,10-phenanthrolene (18mg, 0.1mmol) in 5ml dichlorobenzene stir 48h at 130 DEG C.Then this mixture is concentrated under vacuo, and by this resistates by purification by silica gel column chromatography, to provide title compound (120mg, productive rate: 30%).
1HNMR(300Mz,CDCl
3):δ1.39(t,3H),3.29(q,2H),7.00(dd,1H),7.46(d,1H),7.94(s,1H),8.27(d,1H),8.42(s,1H),8.47(d,1H)；
19FNMR(300Mz,CDCl
3):δ-69.33(s,3F),-64.83(s,3F)；ESI-MS(+):392(M+H)
+。
step e: 2-[2-ethylsulfonyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl) imidazo [1,2-
a] pyridine (compound V3.05):
By compound 2-[2-Ethylsulfanyl-6-(trifluoromethyl)-3-pyridyl]-7-(trifluoromethyl) imidazo [1,2-a] pyridine (156mg, 0.4mmol) stir 2 hours with the mixture of m-CPBA (277mg, 1.6mmol) in 10ml methylene dichloride in envrionment temperature.Then this mixture is poured into NaHCO
3and Na
2sO
3in the saturated solution of Yu Shuizhong, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (115mg, productive rate: 68%).
1H-NMR(300Mz,CDCl
3):δ1.50(t,3H),3.74(q,2H),7.01(dd,1H),7.95(s,1H),7.96(d,1H),8.27(d,1H),8.77(s,1H),8.92(d,1H)；
19FNMR(300Mz,CDCl
3):δ-73.07(s,3F),-69.08(s,3F)；ESI-MS(+):424(M+H)
+。Mpt.188 DEG C of-190 DEG C of LCMS (method SQD13): Rt.1.07 minute, 424 (M+H).
example P11:3-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-
1,2,5-thiadiazoles (compd A 1.014-B8.012):
steps A: (2Z)-2-cyano group-2-oximido-ethyl acetate:
At room temperature, by H
3pO
4(1.83mL, 27mmol) adds ethyl cyanacetate (5g, 44.2mmol) and NaNO to
2in (2.87g, 41.5mmol) mixture in 35ml water.After the addition, this mixture heated to 40 DEG C and stir one hour again.Then, 3.69ml hydrochloric acid is added in this mixture, and continue stirring 18 hours.By this mixture diethyl ether three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (4.3g, productive rate: 69%).
1HNMR(300Mz,DMSO-d
6):δ1.28(t,3H),4.32(q,2H)。
step B:2-amino-2-cyano-acetic acid ethyl ester:
By Na
2s
2o
4(17g, 105mmol) slowly adds to (2Z)-2-cyano group-2-oximido-ethyl acetate (5g, 35mmol) and NaHCO
3in (1.5g, 17mmol) mixture in 40ml water.Then this mixture at room temperature stirred 16h and use chloroform extraction three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo, to provide title compound (3.18g, productive rate 71%).
1HNMR(300Mz,DMSO-d
6):δ1.24(t,3H),3.53(s,2H),4.19(q,2H),4.81(s,1H)。
chloro-1,2, the 5-thiadiazoles-3-ethyl formate of step C:4-:
At ambient temperature, disulphur dichloride (4.06g, 30mmol) is added in the solution of 2-amino-2-cyano-acetic acid ethyl ester (1.28g, 10mmol) in 10mlDMF.This mixture is stirred 16h at ambient temperature and pours in ice, with dichloromethane extraction three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (1.2g, productive rate: 63%).
1HNMR(300Mz,DMSO-d
6):δ1.35(t,3H),4.39(q,2H)。
step D:4-Ethylsulfanyl-1,2,5-thiadiazoles-3-ethyl formate:
By the Na in 10ml water
2s9H
2o (2.4g, 10mmol) to be added in the solution of chloro-1,2,5-thiadiazoles-3-ethyl formate (1.92g, 10mmol) of 4-in 30ml ethanol and by this mixture backflow 4h.Then this mixture concentrated under vacuo and add the solution of monobromethane (3.24g, 30mmol) in 10mlDMF.This reaction mixture is stirred 16 hours in envrionment temperature, pours in dilute hydrochloric acid, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (1.57g, productive rate: 72%).
1HNMR(300Mz,DMSO-d
6):δ1.34(t,3H),1.36(t,3H),3.19(q,2H),4.37(q,2H)；ESI-MS(+):219(M+H)
+,241(M+Na)
+。
step e: 4-Ethylsulfanyl-1,2,5-thiadiazoles-3-carboxylic acid:
By 4-Ethylsulfanyl-1,2,5-thiadiazoles-3-ethyl formate (680mg, 3.12mmol) and LiOH (240mg, 10mmol), the mixture in 5ml water and 5mlTHF at room temperature stirs 2h.Then, this reaction mixture is poured in dilute hydrochloric acid, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide product title compound (550mg, productive rate: 93%).
1HNMR(300Mz,DMSO-d
6):δ1.35(t,3H),3.12(q,2H)。
step F: 3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-1,2,
5-thiadiazoles (compd A 1.014-B8.010):
By 4-Ethylsulfanyl-1,2,5-thiadiazoles-3-carboxylic acid (570mg, 3mmol), N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamines (669mg, 3.5mmol, as prepared in WO2012092051) and the mixture backflow 16h of EDC.HCl (672mg, 3.5mmol) in 5ml pyridine.Then this mixture is concentrated under vacuo, and by purification by silica gel column chromatography, to provide title compound (621mg, productive rate: 60%).
1H-NMR(300Mz,DMSO-d
6):δ1.41(t,3H),3.27(q,2H),4.24(s,3H),8.73(s,1H),8.90(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-53.72(s,3F)；ESI-MS(+):346(M+H)
+。LCMS (method SQD13): Rt.1.21 minute, 346 (M+H) Mpt.188 DEG C-189 DEG C.
step G:3-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4,5-b] pyridine-2-base]-1,2,
5-thiadiazoles (compd A 1.014-B8.012):
By 3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl) imidazo [4 in 10mlDCM, 5-b] pyridine-2-base]-1,2,5-thiadiazoles (0.87mmol, 300mg) at room temperature stir 4h with m-CPBA (519mg, 3mmol).Then this mixture is poured into NaHCO
3and Na
2sO
3in the saturated solution of Yu Shuizhong, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By this resistates by purification by silica gel column chromatography, to provide title compound (147mg, 75%).
1HNMR(300Mz,DMSO-d
6):δ1.31(t,3H),3.97(q,2H),4.00(s,3H),8.76(s,1H),8.94(s,1H)；
19FNMR(300Mz,DMSO-d
6):δ-53.85(s,3F)；ESI-MS(+):378(M+H)
+,400(M+Na)
+,432(M+Na+MeOH)
+。LCMS (method SQD13): Rt.0.93 minute, 378 (M+H) Mpt.144 DEG C-146 DEG C
example P12:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) [1,2,4] three
azoles is [1,5-c] pyrimidine (compound V16.03) also:
steps A: 4-(trifluoromethyl) pyrimidine-1--1,6-diamines, 2,4,6-tri-methyl p-toluenesulfonate salt (MSH):
attention:mSH as dry powder is explosive instability, and preferably processes in dichloromethane solution.
2,2,2-trifluoroacetic acid (4.4g, 2.54mmol, 2.9mL) is loaded the microwave tube being equipped with a magnetic stirring bar.Then, at 0 DEG C of interpolation (t-butoxycarbonyl amino) 2,4,6-tri-methyl p-toluenesulfonate salt (1g, 2.54mmol).This reaction mixture is stirred 2h at 0 DEG C, adds ice-water, and by filtered and recycled throw out.Wet cake is washed with water, and is dissolved in methylene dichloride (5mL), and use dried over sodium sulfate.At 0 DEG C, in the stirred solution of 6-(trifluoromethyl) pyrimidine-4-amine (0.3723g, as prepared in WO2007113558) in methylene dichloride (5mL), dropwise add gained solution.At 0 DEG C after 1 hour and the at room temperature night (white suspension), by diethyl ether (8mL) dilution of this reaction mixture, and by filtered and recycled throw out, to obtain title compound (0.791g, 82%).
step B:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl)-[1,2,4] triazole
and [1,5-c] pyrimidine (compound V16.03):
4-(trifluoromethyl) pyrimidine-1--1; 6-diamines; 2; 4,6-tri-methyl p-toluenesulfonate salt (0.3g, 0.791mmol), 3-ethylsulfonyl-5-(trifluoromethyl) pyridine-2-carboxylic acids (0.33593g; 1.1861mmol) with 3-(ethylimino methene amido)-N; N-dimethyl-propyl-1-amine salt acidulants (0.1819098g, 0.9489mmol) is dissolved in pyridine (2mL), and at 120 DEG C of heating 3h.At this moment after, this reaction mixture is poured onto waterborne, by aqueous extracted with EtOAc three times.By the organic layer priority water of merging and salt water washing, use Na
2sO
4drying, filters and concentrates under vacuo.Crude product diethyl ether is ground and filters, to provide the product (110mg, 33%) in white powder.
1HNMR(400MHz,CDCl3):δ(ppm)9.31(d,J＝2.2Hz,1H),9.17(d,J＝1.5Hz,1H),8.34-8.53(m,1H),3.23(q,J＝7.5Hz,2H),1.37(t,J＝7.5Hz,3H)。LCMS (method SQD13): Rt:0.94min, 426 (M+H).Mpt.:190℃-192℃
example P13:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) oxazole also [5,
4-c] pyridine (compound V12.05):
steps A: 4-nitro-6-(trifluoromethyl) pyridine-3-alcohol:
At 0 DEG C, in the solution of 6-(trifluoromethyl) pyridine-3-alcohol (5.00g, 30.7mmol) in sulfuric acid (92.0mL), add ice (25.0g, 1390mmol), temperature is remained on less than 10 DEG C.Nitric acid (2.97g, 2.14mL, 30.7mmol) is added in this solution, and by this mixture 85 DEG C of heating 4 hours.Add the nitric acid (2.97g, 2.14mL, 30.7mmol) of second section, and this reaction is spent the night 85 DEG C of stirrings.Lcms analysis display about 40% transforms, and therefore adds nitric acid (2.97g, 2.14mL, 30.7mmol), and this reaction is stirred 5h at 85 DEG C.Add the nitric acid (2.97g, 2.14mL, 30.7mmol) of another part, and this reaction is spent the night 85 DEG C of stirrings.At this moment, after, this mixture to be poured in frozen water and to use 250mlEt
2o extracts.Also concentrate dry for the organic phase with sodium sulfate of merging under vacuo.By this resistates by flash chromatography, with dichloromethane eluent, to provide title compound (18% productive rate).
1HNMR(400MHz,CDCl3):10.32(s,1H),8.82(s,1H),8.30(s,1H)ppm。
step B:4-amino-6-(trifluoromethyl) pyridine-3-alcohol:
Under argon, in the solution of 4-nitro-6-(trifluoromethyl) pyridine-3-alcohol (1.15g, 5.53mmol) in ethanol (50mL) and tetrahydrofuran (THF) (10mL), add palladium carbon (0.12g).Application nitrogen atmosphere (balloon), and this mixture is at room temperature stirred spend the night.After completing reduction, by this mixture diatomite filtration, and by filter cake washing with alcohol.Solvent to be removed under vacuo and by this resistates by flash chromatography (cyclohexane/ethyl acetate) purifying, take on a red color title compound gluey to provide (0.98g, quantitatively).
1HNMR(400MHz,CDCl3):7.92(s,1H),6.92(s,1H),4.75(s,2H)ppm。
step C:2-[3-Ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) oxazole also [5,4-
c] pyridine.(compd A 6.006-B1.014):
By 4-amino-6-(trifluoromethyl) pyridine-3-alcohol (100mg, 0.56mmol) with 3-Ethylsulfanyl-5-(trifluoromethyl) pyridine-2-carboxylic acids (155mg, 0.62mmol, as prepared in WO2013018928) solution in Tripyrophosphoric acid (2mL) stirs 24 hours at 185 DEG C.Then with vigorous stirring this reaction mixture is poured in water (50mL), and pH NaOH (2N) is adjusted to 8.By aqueous phase methylene dichloride (x2) extraction, and by dry for the organic phase with sodium sulfate merged.This solvent of vaporising under vacuum, and by this resistates by flash chromatography (cyclohexane/ethyl acetate) purifying, to provide title compound (75mg, 34%).
1HNMR(400MHz,CDCl3):9.20(s,1H),8.82(s,1H),8.32(s,1H),7.98(s,1H),3.14(q,2H),1.54(t,3H)ppm。LCMS (method SQD13): Rt:1.15min, 394 (M+H).
step D:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) oxazole also [5,4-
c] pyridine (compound V12.05):
To 2-[3-Ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) oxazole also [5,4-c] pyridine (60mg, m-CPBA (83mg, 0.34mmol) is added in solution 0.153mmol) in methylene dichloride (10mL).By gained yellow solution stirring at room temperature 1 hour, and and then add 60mgm-CPBA.This reaction mixture is stirred 2h again in room temperature, and then pours in the saturated solution of salt of wormwood.By aqueous phase dichloromethane extraction twice, and by dry for the organic phase with sodium sulfate merged, and concentrate under vacuo.By this resistates by flash chromatography (cyclohexane/ethyl acetate) purifying, to provide the title compound (49mg, 75%) (75%) in white powder.
1HNMR(400MHz,CDCl
3):9.28(s,1H),9.22(s,1H),8.84(s,1H),8.24(s,1H),3.98(q,2H),1.48(t,3H)ppm。LCMS (method SQD13): Rt.1.02min, 426 (M+H+).
example P14:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) imidazo [1,
2-c] pyrimidine (compound V16.02):
steps A: 1-[3-Ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl] ethyl ketone:
By bromine (methyl) magnesium, (1.4M is in THF: in toluene 1:3,14Ml, solution 18.95mmol) in the toluene (90mL) of drying is cooled to 0 DEG C, and dropwise use 3-Ethylsulfanyl-5-(trifluoromethyl) pyridine-2-formonitrile HCN (4.00g, 17.23mmol, as prepared in WO2013018928) solution be dissolved in 30ml toluene processes.This reaction is allowed to stir 30min at 0 DEG C.At this moment, after, lcms analysis display reaction completes.This reaction mixture is slowly used NH
4the saturated water-based of Cl (50ml) and HCl10% (30ml) cancellation, and by gained mixture at room temperature vigorous stirring 15min.By aqueous extracted with EtOAc twice, and by the organic phase of merging successively with 10% water-based HCl, water and salt water washing, use anhydrous Na
2sO
4drying, filters and concentrates under vacuo.By not purified for next step for thick title product (4.335g, 91%).
1HNMR(400MHz,CDCl
3):δ(ppm)8.62(s,1H),7.85(d,J＝1.1Hz,1H),2.96(q,J＝7.3Hz,2H),2.74(s,3H),1.43(t,J＝7.5Hz,3H)。LCMS (method SQD13): retention time 1.05min, 250 (M+H).
step B:1-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl] ethyl ketone:
At 0 DEG C, by m-CPBA (24.29g, 98.53mmol) be added in 1-[3-Ethylsulfanyl-5-(the trifluoromethyl)-2-pyridyl] solution of ethyl ketone (11.98g, 48.06mmol) in chloroform (400mL) (at 0 DEG C) by part.Gained mixture is allowed to heat to room temperature and stir 20h.Then by this reaction mixture 200mL water-based NaHCO
3with the cancellation of 50mL saturated aqueous sodium thiosulfate, and extract three times with EtOAc.By the organic phase successively use NaHCO merged
3with salt water washing, use Na
2sO
4drying also concentrates under vacuo.On 220g post on mighty torrent machine (torrentmachine), purifying (with EtOAc/ heptane wash-out), provides the title compound (8.5g, 63%) in white solid.
1HNMR(400MHz,CDCl
3):δ(ppm)9.07(d,J＝1.1Hz,1H),8.59(d,J＝1.5Hz,1H),3.58(q,J＝7.3Hz,2H),2.74(s,3H),1.38(t,J＝7.5Hz,3H)。LCMS (method SQD13): retention time 0.87min, 282 (M+H).
step C:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) imidazo [1,2-
c] pyrimidine:
By 6-(trifluoromethyl) pyrimidine-4-amine (232mg; 1.0607mmol; as prepared in WO2007113558), 1-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl] ethyl ketone (200mg; 0.71mmol), cupric iodide (I) (7.0mg; 0.036mmol), the mixture of trifluoromethayl sulfonic acid In (III) (4.0mg, 0.0071mmol) and 1-Methyl-2-Pyrrolidone (4mL) stirs 19 hours at 120 DEG C.LC-MS: desired product and parent material, and thus this reaction is stirred 27 hours again at 120 DEG C.Reaction mixture is cooled to envrionment temperature, and adds water and ethyl acetate.Aqueous layer with ethyl acetate is extracted 2 times, and the organic layer washed with brine that will merge, use Na
2sO
4drying, filters and concentrates under vacuo.This product is carried out purifying by combiflash chromatography with the gradient of the post of 12g and hexanaphthene+0-80% ethyl acetate, to provide the title compound (96mg, 31%) in white solid.
1HNMR(400MHz,CDCl
3):δ(ppm)9.20(s,1H),9.14(s,1H),8.80(d,J＝1.5Hz,1H),8.44(s,1H),7.99(s,1H),4.10(q,J＝7.5Hz,2H),1.43(t,J＝7.5Hz,3H)。LCMS (method SQD13): Rt:0.98min, 425 (M+H).Mpt.180℃-181℃。
example P15:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-7-(trifluoromethyl) miaow
azoles is [1,2-c] pyrimidine (compound V16.01) also:
the bromo-2-of steps A: 3-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) imidazo
[1,2-c] pyrimidine:
By 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) imidazo [1; 2-c] pyrimidine (52mg; 0.123mmol) be dissolved in acetonitrile (1mL); and use N-bromosuccinimide (24.5mg, 0.135mmol) to process at ambient temperature.By reaction mixture in stirred overnight at room temperature.This reaction mixture is concentrated under vacuo, and carries out purifying by combiflash chromatography with the gradient of the post of 4g and hexanaphthene+0-50% ethyl acetate.Obtain the title product in white solid.
1HNMR(400MHz,CDCl
3):δ(ppm)9.22(d,J＝0.7Hz,1H),9.20(s,1H),8.77(d,J＝1.5Hz,1H),7.94(s,1H),4.00(q,J＝7.6Hz,2H),1.40-1.47(t,J＝7.6Hz,3H)。LCMS (method SQD13): Rt:1.04min, 503/505 (M+H).
the bromo-2-of step B:3-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) imidazo
[1,2-c] pyrimidine (compound V16.01):
By bromo-for 3-2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-(trifluoromethyl) imidazo [1; 2-c] pyrimidine (100mg; 0.199mmol) with salt of wormwood (84mg; 0.60mmol) in 1; suspension argon in 4-diox (3mL) purges 10min; and then use 2,4,6-trimethylammonium-1; 3; 5,2,4; 6-trioxa three boron azacyclohexane (trioxatriborinane) (30.0mg; 0.24mmol, 0.0332mL) and Pd (Ph3) 4 (23mg, 0.02mmol) process.This reaction mixture is heated 12 hours at 95 DEG C.Product desired by lcms analysis display and parent material, and thus this mixture cooled and purge 10min with argon, and with 2,4,6-trimethylammonium-1,3,5,2,4,6-trioxa three boron azacyclohexane (trioxatriborinane) (30.0mg, 0.24mmol, 0.0332mL) with Pd (Ph3) 4 (23mg, 0.02mmol) process.This reaction mixture is reheated 5 hours until reacted at 95 DEG C.By this reaction mixture NH
4cl saturated solution and water dilution, and be then extracted with ethyl acetate three times.By the organic layer washed with brine merged, use Na
2sO
4drying, filters and concentrates under vacuo.Product is carried out purifying by combiflash chromatography with the gradient of the post of 12g and hexanaphthene 0-50% ethyl acetate.This provides the title product (51mg, 59%) in white solid.
1hNMR (400MHz, CDCl
3): δ (ppm) 9.17 (d, J=1.5Hz, 1H), 9.01 (s, 1H), 8.77 (d, J=1.5Hz, 1H), 4.10 (q, J=7.6Hz, 2H), 2.78 (s, 3H), 1.40-1.47 (t, 7.6Hz, 3H) .LCMS (method SQD13): Rt:1.01min, 439 (M+H).Mpt.240℃-242℃。
example P16:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-1-methyl-5-(trifluoromethyl) miaow
azoles is [4,5-b] pyrazine (compd A 1.026-B1.022) also:
the iodo-N-Methyl-pyrazin of steps A: 3,5-bis--2-amine:
At 10 DEG C, to N-methylpyrazine-2-amine (1g, 9.2mmol) in methyl-sulphoxide (20ml)/water (0.4ml) in stirred solution in by part add N-iodine succinimide (4.1g, 18.4mmol).Then allow this reaction mixture slowly to heat to room temperature and stir at such a temperature to spend the night.Then the other aliquots containig of N-iodine succinimide (4.1g, 18.4mmol) is at room temperature added.After stirring 7 hours, this reaction mixture is poured onto on ice (20g).Collecting precipitation thing, with cold water (20ml) washing, and dry, to provide title compound (2.15g, 65%).
1HNMR(300MHz,DMSO-d
6)δ(ppm)：8.14(s,1H),6.69(br,1H),2.77(d,3H,J＝4.5Hz)；ESI-MS(-):360。
step B:5-iodo-N2-Methyl-pyrazin-2,3-diamines:
By the NH in EtOH (15ml)
3(gas) is added in 3,5-bis-iodo-N-Methyl-pyrazin-2-amine (2.15g, 6mmol), and in sealed tube, this mixture is heated to 150 DEG C of lasting 18h.After this solution of cooling, add methylene dichloride and water (1:1,200ml).By aqueous phase methylene dichloride (50ml) extraction, and by the organic layer Na of merging
2sO
4drying is also concentrated, to provide the title compound in white solid.(1.19g，80％)。
1HNMR(300MHz,DMSO-d
6)δ(ppm)：7.41(s,1H)6.35(br,3H),2.78(s,3H)；ESI-MS(-):249,ESI-MS(+):251。
step C:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl] the iodo-1-methyl-imidazoles of-5-also [4,5-
b] pyrazine:
By the method described in above example, from 5-iodo-N2-Methyl-pyrazin-2,3-diamines and 3-ethylsulfonyl-5-(trifluoromethyl) pyridine-2-carboxylic acids, prepare this compound.
step D:2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-1-methyl-5-(trifluoromethyl) imidazoles
and [4,5-b] pyrazine (compd A 1.026-B1.022):
By compound 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl] the iodo-1-methyl-imidazoles of-5-also [4,5-b] pyrazine (497mg, 1mmol), FSO
2cF
2cOOMe (384mg, 2mmol) and the mixture of CuI (191mg, 1mmol) in 5mlDMF stir 24h under nitrogen atmosphere at 120 DEG C.Then, this mixture is poured in dilute hydrochloric acid, and be extracted with ethyl acetate three times.By dry for the organic layers with sodium sulfate merged, filter and concentrate under vacuo.By crude product by purification by silica gel column chromatography, to provide title compound (197.5mg, productive rate: 45%).
1HNMR(300MHz,CDCl
3)δ(ppm)：9.26(s,1H),8.88(s,1H),8.75(s,1H),3.98(m,5H),1.42(t,J＝6.9Hz,3H)。
19FNMR(300Mz,CDCl
3)δ(ppm)：-62.15；-65.18。ESI-MS:440(M+H),462(M+Na
+)。Mpt.162℃-165℃。LCMS (method SQD13): Rt.1.04 minute, 440 (M+H).
example P17:3-methyl-2-[3-(sulfonyloxy methyl ylmethyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoro
methyl) imidazo [4,5-b] pyridine (compd A .014-B1.106):
By 3-methyl-5-(trifluoromethyl) pyridine-2-ethyl formate (1.0g4.29mmol, as at JACS (J.Amer.Chem.Soc.), 2013,135, prepare described in 12122-12134) be dissolved in acetonitrile (40ml), and process with N-bromine succinic diamide (1.21g, 6.43mmol) and benzoyl peroxide (0.150g, 0.600mmol).Sun lamp is used to irradiate this reaction mixture, by its reflux (75 DEG C of bath temperature).After 10 hours, this mixture is cooled, filter, and concentrate under vacuo.By crude product (1.27g) (it mainly comprises 3-(brooethyl)-5-(trifluoromethyl) pyridine-2-ethyl formate) without being further purified for next step.
3-(brooethyl)-5-(trifluoromethyl) pyridine-2-ethyl formate (0.5g, 1.6mmol, above preparation) is dissolved in DMF, is cooled to 0 DEG C, and processes with sodium methyl mercaptide (0.22g, 3.2mmol).Allow this mixture to heat to room temperature, and stirring is spent the night.By this reaction mixture use NH
4cl dilutes, and extracts with TBME (2x).By the 6N water-based HCl acidifying of the water layer of remainder, and with dichloromethane extraction 3 times.By the dichloromethane layer Na of merging
2sO
4drying, filters and evaporates, and to provide 0.31g buff white solid, this solid comprises desired 3-(methylsulfanyl methyl)-5-(trifluoromethyl) pyridine-2-carboxylic acids.By it without being further purified for next step.
By N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamines (0.24g, 1.3mmol, as prepared in WO2012092051), EDC.HCl (0.24g, 1.3mmol) be dissolved in pyridine (15ml) with 3-(methylsulfanyl methyl)-5-(trifluoromethyl) pyridine-2-carboxylic acids (0.29g, the crude samples from above).This brown suspension is stirred 2h at 120 DEG C.By this reaction mixture dilute with water, and extract with EtOAc.Be separated organic layer, and use salt water washing, use Na
2sO
4drying is also evaporated.By crude product by RF200 machine chromatography (with EtOAc/ hexanaphthene gradient elution) purifying, to provide 0.35g buff white solid, this solid comprises desired product N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-3-(methylsulfanyl methyl)-5-(trifluoromethyl) pyridine-2-carboxamide.This product is dissolved in 1-methylpyrrolidin-2-ketone (5ml) of toluene-4-sulfonic acid (0.072g, 0.41mmol), and at 160 DEG C of heating 1h in microwave.At this moment, after, by this reaction mixture dilute with water, and extract with EtOAc.By organic layers with water and salt water washing, also concentrate under vacuo by dried over sodium sulfate.With silica gel barrel mast (Rf200) purifying, with hexanaphthene/EtOAc wash-out, provide 3-methyl-2-[3-(methylsulfanyl methyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) imidazo [4, the 5-b] pyridine (140mg) in white solid.LCMS (method SQD13): Rt.1.17 minute, 407 (M+H).
By 3-methyl-2-[3-(methylsulfanyl methyl)-5-(trifluoromethyl)-2-pyridyl]-6-(trifluoromethyl) imidazo [4,5-b] pyridine (100mg, solution 0.25mmol) in methylene dichloride is cooled to 0 DEG C, and add MCPBA (61mg, 0.25mmol) at 0 DEG C.After 1h, LC/MS shows sulfoxide and sulfone, and adds 61mgMCPBA more thus.When reaction completes, by this mixture 2MNa
2cO
3with methylene dichloride cancellation.Be separated organic layer, wash with water once, use Na
2sO
4drying, filters and concentrates under vacuo.With silica gel barrel mast (Rf200) purifying, with hexanaphthene/EtOAc wash-out, provide the title compound (80mg, 70%) in white solid.LCMS (method SQD13): Rt.1.02 minute, 439 (M+H).
1HNMR(400MHz,CDCl
3):δ(ppm)9.08(d,J＝1.5Hz,1H),8.79(d,J＝1.5Hz,1H),8.34-8.36(m,1H),8.33(d,J＝1.8Hz,1H),5.25(s.,2H),4.13(s,3H),2.93(s,3H)。
the bromo-2-of example P18:6-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-imidazoles also [4,
5-c] pyridine (compound V12.20):
the fluoro-1-oxidation-pyridine of the bromo-5-of steps A: 2--1-:
At 0 DEG C, in the stirred solution of 2-bromo-5-fluorine pyridine (5.0g, 28.4mmol) in TFA (10.0mL), dropwise add H
2o
2(30%, 15mL), stirs this mixture under reflux and spends the night.After cooling, this reactive system is poured onto ice-waterborne, with methylene chloride/methanol (10:1,50mLx3) extraction, by organic layer saturated sodium bicarbonate solution and salt water washing, and uses anhydrous sodium sulfate drying.In filtration with after concentrating under vacuo, by crude product (pale solid, 4.6g, productive rate: 84%) without being further purified for next step.
the fluoro-4-nitro of the bromo-5-of step B:2--1-oxidation-pyridine-1-:
At 0 DEG C, in the solution of 2-bromo-5-fluoro-1-oxidation-pyridine-1-(4.6g, 23.9mmol) in sulfuric acid (dense) (20mL), slowly add nitrosonitric acid (10mL).After the addition, this temperature of reaction rises to 120 DEG C, and continues at this temperature to stir 4h.After cooling to room-temperature, this reaction soln is poured onto ice-waterborne.By pH value NH
4oH is adjusted to 1.Filtering precipitate, and oven drying, to obtain the title compound (2.3g, 40%) in faint yellow solid shape.
the bromo-N-methyl of step C:6--4-nitro-1-oxidation-pyridine-1--3-amine:
MeNH is added in the solution of 2-bromo-5-fluoro-4-nitro-1-oxidation-pyridine-1-(1.1g, 4.6mmol) in ethanol (10mL)
2/ ethanol (4mL).By this reaction mixture at stirring at room temperature 4h.This mixture is concentrated under vacuo, to provide the title compound in solid state, by it without being further purified for next step.
the bromo-N-methyl of step D:6--4-nitro-pyridine-3-amine:
PBr (1.0mL) is added in the solution of 6-bromo-N-methyl-4-nitro-1-oxidation-pyridine-1--3-amine (from above thick, 4.6mmol) in methylene dichloride (10mL).This reaction mixture is stirred 1 hour at ambient temperature.This mixture is dry under vacuo, to provide the title compound in orange solid state, and by it without being further purified for next step.
step e: 6-bromo-N3-methvl-pyridinium-3,4-diamines:
To the bromo-N-methyl of 6--4-nitro-pyridine-3-amine (crude product, add in solution 4.6mmol) in methyl alcohol (10mL) Raney's nickel (RaneyNi) (20%wt), and dropwise add hydrazine hydrate (1.0mL) at 0 DEG C.This reaction mixture is at room temperature stirred several minutes.Raney's nickel (RaneyNi) is fallen by diatomite filtration; Filtrate is dry under vacuo, and with silica gel column chromatography (methylene dichloride: methyl alcohol, 10:1) purifying, to obtain the title compound (0.6g, three step productive rates, 63%) in lavender solid state.
1HNMR(400MHz,DMSO-d
6):δ(ppm)7.20(s,1H),6.65(s,1H),6.54(brs,2H),3.34(s,1H),2.69(d,J＝6.4Hz,3H)。ESI-MS(+):203(M+H)。
step F: N-(the bromo-3-pyridyl of 4-amino-6-)-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl) pyridine-
2-methane amide:
To the bromo-N3-methvl-pyridinium-3 of 6-; 4-diamines (0.60g; 2.96mmol), 3-ethylsulfonyl-5-(trifluoromethyl) pyridine-2-carboxylic acids (0.92g; 3.26mmol; as prepared in WO2013180194) and HATU (1.4g; DIPEA (1.2ml, 7.26mmol) is added in stirred solution 3.68mmol) in DMF (5.0mL).This system is at room temperature stirred and spends the night.By this reaction EtOAc and H
2o dilutes, and by organic layer washed with brine and water washing, uses anhydrous sodium sulfate drying.In filtration with after concentrating under vacuo, by this thick title product without being further purified for next step.
the bromo-2-of step G:6-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-imidazoles also [4,5-
c] pyridine (compound V12.20):
The solution of N-(the bromo-3-pyridyl of 4-amino-6-)-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl) pyridine-2-carboxamide (crude product, 2.96mmol) in acetic acid (5.0mL) is spent the night 120 DEG C of stirrings.This mixture is evaporated to drying.By this resistates by purified on silica (sherwood oil: EtOAc=4:1), to obtain title compound (0.65g, the two step productive rates: 48%) in white solid.
1HNMR(400MHz,DMSO-d
6):δ(ppm)9.53(s,1H),8.94(s,1H),8.74(s,1H),8.01(s,1H),3.83(q,J＝7.6Hz,2H),3.79(s,3H),1.19(t,J＝7.2Hz,3H)。
19FNMR(300MHz,DMSO-d6):δ(ppm)-60.42(s,3F)。ESI-MS(+):449(M+H),472(M+Na)；ESI-MS(-):447(M-H)。Mpt.188℃-190℃。LCMS (method SQD13): Rt.0.95min, 451 (M+H).
the chloro-6-of example P19:3-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazoles also [4,
5-c] pyridazine (compound V12.17)
steps A: 3,6-dichloro-pyridazine-4-amine
Bromo-for 4-3,6-bis-chloro-pyridazines (15.0g, 65.8mmol, as prepared in WO2008116815) are dissolved in EtOH (73.1mL), and are incorporated in autoclave.At room temperature, the NH of gas is introduced
3(4.48g, 263mmol), and then this reaction mixture is stirred under reflux and spend the night.This solution is concentrated under vacuo, and this resistates EtOAc is ground, insoluble Partial filtration is fallen, and mother liquid evaporation, to provide crude product.Passed through flash chromatography, with hexanaphthene/EtOAc1/1+2.5%Et3N wash-out, to provide the title compound (5.82g, 53%) in light brown solid.LCMS (method ZCQ13): Rt.0.3min, 164/166/168 (M+H).
step B:6-chloro-N3-methyl-pyridazin-3,4-diamines
In autoclave, by 3,6-dichloro-pyridazine-4-amine (2.35g, 14.3mmol) the methylamine process be dissolved in EtOH (20.2g, 215mmol, 26.7mL), and be heated to 100 DEG C.At 100 DEG C after 48h, LCMS no longer shows parent material.This reaction mixture is evaporated to drying.This crude product is diluted in methylene dichloride, and adds 4mlEt
3n.This mixture is at room temperature stirred 5' and evaporates.By the 5ml water dilution of this resistates, and by insoluble filtration of material, and dry, to provide the title product (1.35g, 57%) in light brown solid.LCMS (method ZCQ13): Rt.0.17min, 157/159 (M-H).
step C:N-[the chloro-3-of 6-(methylamino) pyridazine-4-base]-3-Ethylsulfanyl-5-(trifluoromethyl) pyridine-2-
methane amide
The chloro-N3-methyl-pyridazin-3 of 6-in pyridine (14.6mL) will be dissolved in, 4-diamines (0.3g, 1.89mmol) with 3-Ethylsulfanyl-5-(trifluoromethyl) pyridine-2-carboxylic acids (0.499g, 1.99mmol, as prepared in WO2013018928) and EDCI.HCl (0.4352g, 2.27mmol) process.By this reaction mixture at stirring at room temperature 4h, and then use EDCI.HCl (0.4352g, the 2.27mmol) process of part in addition.By this mixture in stirred overnight at room temperature.Then by this reaction mixture reduced under vacuum, and this resistates is absorbed in EtOAc and water.Separation of phases also by this organic phases washed with brine, uses Na
2sO
4drying, and concentrate under vacuo.By this crude product, by Flash-Master, (solvent: hexanaphthene/EtOAc3/1 carries out purifying, to provide the title compound (250mg, 33%) in white solid.LCMS (method ZCQ13) retention time 1.01min, 392/394 (M+H).
the chloro-6-of step D:3-[3-Ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazoles also [4,5- c] pyridazine (compounda6.015-B1.014)
N-[the chloro-3-of 6-(methylamino) pyridazine-4-base]-3-Ethylsulfanyl-5-(trifluoromethyl) pyridine-2-carboxamide (250mg, 0.64mmol) is dissolved in DMF (2mL) and toluene (8mL).Add tosic acid monohydrate (0.123g, 0.70mmol).Close bomb pipe, and be heated to 160 DEG C and continue 4 hours.Then be cooled to room temperature and be evaporated to drying.This resistates is carried out purifying, to provide the title compound (172mg, 72%) in yellow solid by Flash-Master (solvent: hexanaphthene/EtOAc2/1).
1HNMR(400MHz,CDCl
3):δ(ppm)8.65-8.88(m,1H),7.86-8.05(m,2H),4.13-4.27(m,3H),3.04(q,J＝7.5Hz,2H),1.41(t,J＝7.5Hz,3H)。LCMS (method ZCQ13): retention time 1.01min, 374/376 (M+H).Mpt.:156℃-158℃。
the chloro-6-of step D:3-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazoles also [4,5-
c] pyridazine (compound V12.17)
By chloro-for 3-6-[3-Ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-7-methyl-imidazoles also [4,5-c] pyridazine (0.14g, 0.3745mmol) be dissolved in methylene dichloride (8mL).At 0 DEG C, add MCPBA (0.1747g, 0.7491mmol), and this mixture is stirred 1h at 0 DEG C, then at room temperature stir 3h.By this reaction saturated sodium thiosulfate solution cancellation.By the organic phase saturated NaHCO3 and the salt water washing that are separated, use Na
2sO
4drying, filters and concentrates under vacuo.This crude product is carried out purifying, to provide the title compound (164mg, 96%) in white solid by Flash-Master (solvent: hexanaphthene/EtOAc1/1).
1HNMR(400MHz,CDCl
3):δ(ppm)9.28(d,J＝1.5Hz,1H),8.78(d,J＝1.8Hz,1H),7.71-8.03(m,1H),4.02(s,3H),3.84(q,J＝7.6Hz,2H),1.40(t,J＝7.5Hz,3H)。LCMS (method ZCQ13): retention time 0.91min, 406/408 (M+H).Mpt.228℃-229℃。
The concrete example with the compound of chemical formula (I) is shown in following table 1 to 130, and wherein Table A describes group B to K, and shows L to Q and describe group A:
A-B(I)
table Athere is chemical formula B
1group (DB represents a direct key, and namely this sulphur is directly attached to aromatic nucleus)
table B:there is chemical formula B
2group
table C:there is chemical formula B
3group
table D:there is chemical formula B
4group
| Group | R 12 | V 1 | V 2 |
| B4.001 | CH 3 | N | C-H |
| B4.002 | CH 3 | N | C-CF 3 |
| B4.003 | CH 3 | N | C-Br |
| B4.004 | CH 3 | N | C-Cl |
| B4.005 | CH 3 | C-H | C-H |
| B4.006 | CH 3 | C-H | C-CF 3 |
| B4.007 | CH 3 | C-H | C-Br |
| B4.008 | CH 3 | C-H | C-Cl |
table E:there is chemical formula B
5group
table F:there is chemical formula B
6group
| Group | R 19 | V 1 | V 2 |
| B6.001 | C(CH 3) 3 | N | C-H |
| B6.002 | C(CH 3) 3 | N | C-CF 3 |
| B6.003 | C(CH 3) 3 | N | C-Br |
| B6.004 | C(CH 3) 3 | N | C-Cl |
| B6.005 | C(CH 3) 3 | C-H | C-H |
| B6.006 | C(CH 3) 3 | C-H | C-CF 3 |
| B6.007 | C(CH 3) 3 | C-H | C-Br |
| B6.008 | C(CH 3) 3 | C-H | C-Cl |
| B6.009 | H | N | C-H |
| B6.010 | H | N | C-CF 3 |
| B6.011 | H | N | C-Br |
| B6.012 | H | N | C-Cl |
| B6.013 | H | C-H | C-H |
| B6.014 | H | C-H | C-CF 3 100 --> |
| B6.015 | H | C-H | C-Br |
| B6.016 | H | C-H | C-Cl |
table G:there is chemical formula B
7group
table H:there is chemical formula B
8group
| Group | R 3 | V 5 | V 6 | m |
| B8.001 | CH 3 | C-H | C-H | 0 |
| B8.002 | CH 3 | C-H | C-H | 1 |
| B8.003 | CH 3 | C-H | C-H | 2 |
| B8.004 | CH 2CH 3 | C-H | C-H | 0 |
| B8.005 | CH 2CH 3 | C-H | C-H | 1 |
| B8.006 | CH 2CH 3 | C-H | C-H | 2 |
| B8.007 | CH 3 | C-H | N | 0 |
| B8.008 | CH 3 | C-H | N | 1 |
| B8.009 | CH 3 | C-H | N | 2 |
| B8.010 | CH 2CH 3 | C-H | N | 0 |
| B8.011 | CH 2CH 3 | C-H | N | 1 |
| B8.012 | CH 2CH 3 | C-H | N | 2 |
table I:there is chemical formula B
9group
| Group | R 3 | V 8 | V 7 | m |
| B9.001 | CH 3 | C-H | C-H | 0 |
| B9.002 | CH 3 | C-H | C-CF 3 | 0 |
| B9.003 | CH 3 | C-H | C-Br | 0 |
| B9.004 | CH 3 | C-H | C-Cl | 0 |
| B9.005 | CH 3 | C-H | C-H | 1 |
| B9.006 | CH 3 | C-H | C-CF 3 | 1 |
| B9.007 | CH 3 | C-H | C-Br | 1 |
| B9.008 | CH 3 | C-H | C-Cl | 1 |
| B9.009 | CH 3 | C-H | C-H | 2 |
| B9.010 | CH 3 | C-H | C-CF 3 | 2 |
| B9.011 | CH 3 | C-H | C-Br | 2 |
| B9.012 | CH 3 | C-H | C-Cl | 2 |
| B9.013 | CH 2CH 3 | C-H | C-H | 0 |
| B9.014 | CH 2CH 3 | C-H | C-CF 3 | 0 |
| B9.015 | CH 2CH 3 | C-H | C-Br | 0 |
| B9.016 | CH 2CH 3 | C-H | C-Cl | 0 |
| B9.017 | CH 2CH 3 | C-H | C-H | 1 |
| B9.018 | CH 2CH 3 | C-H | C-CF 3 | 1 |
| B9.019 | CH 2CH 3 | C-H | C-Br | 1 |
| B9.020 | CH 2CH 3 | C-H | C-Cl | 1 |
| B9.021 | CH 2CH 3 | C-H | C-H | 2 |
| B9.022 | CH 2CH 3 | C-H | C-CF 3 | 2 |
| B9.023 | CH 2CH 3 | C-H | C-Br | 2 |
| B9.024 | CH 2CH 3 | C-H | C-Cl | 2 |
| B9.025 | CH 3 | C-H | N | 0 |
| B9.026 | CH 3 | C-H | N | 1 |
| B9.027 | CH 3 | C-H | N | 2 |
| B9.028 | CH 2CH 3 | C-H | N | 0 |
| B9.029 | CH 2CH 3 | C-H | N | 1 |
| B9.030 | CH 2CH 3 | C-H | N | 2 |
table J:there is chemical formula B
10group
| Group | R 3 | V 9 | V 10 | V 11 | m |
| B10.001 | CH 2CH 3 | C-H | C-H | C-H | 0 |
| B10.002 | CH 2CH 3 | C-H | C-H | C-H | 1 |
| B10.003 | CH 2CH 3 | C-H | C-H | C-H | 2 |
| B10.004 | CH 2CH 3 | N | C-H | C-H | 0 |
| B10.005 | CH 2CH 3 | N | C-H | C-H | 1 |
| B10.006 | CH 2CH 3 | N | C-H | C-H | 2 |
| B10.007 | CH 2CH 3 | N | C-H | N | 0 |
| B10.008 | CH 2CH 3 | N | C-H | N | 1 |
| B10.009 | CH 2CH 3 | N | C-H | N | 2 |
| B10.010 | CH 2CH 3 | N | N | N | 0 |
| B10.011 | CH 2CH 3 | N | N | N | 1 |
| B10.012 | CH 2CH 3 | N | N | N | 2 |
table K:there is chemical formula B
11group
table L:there is chemical formula A
1group
table M:there is chemical formula A
2group
table N:there is chemical formula A
3group
| Group | R 1 | R 2 | G 1 | G 2 | G 4 |
| A3.001 | CH 3 | H | C-H | C-H | N |
| A3.002 | CF 3 | H | C-H | C-H | N |
| A3.003 | Cl | H | C-H | C-H | N |
| A3.004 | Br | H | C-H | C-H | N |
| A3.005 | CH 3 | H | C-H | N | N |
| A3.006 | CF 3 | H | C-H | N | N |
| A3.007 | Cl | H | C-H | N | N |
| A3.008 | Br | H | C-H | N | N |
| A3.009 | CH 3 | H | N | N | N |
| A3.010 | CF 3 | H | N | N | N |
| A3.011 | Cl | H | N | N | N |
| A3.012 | Br | H | N | N | N |
| A3.013 | CH 3 | H | C-H | C-H | C-CH 3 |
| A3.014 | CF 3 | H | C-H | C-H | C-CH 3 |
| A3.015 | Cl | H | C-H | C-H | C-CH 3 |
| A3.016 | Br | H | C-H | C-H | C-CH 3 |
| A3.017 | CH 3 | H | C-H | N | C-CH 3 |
| A3.018 | CF 3 | H | C-H | N | C-CH 3 |
| A3.019 | Cl | H | C-H | N | C-CH 3 |
| A3.020 | Br | H | C-H | N | C-CH 3 |
| A3.021 | CH 3 | H | N | N | C-CH 3 |
| A3.022 | CF 3 | H | N | N | C-CH 3 |
| A3.023 | Cl | H | N | N | C-CH 3 |
| A3.024 | Br | H | N | N | C-CH 3 |
Table O: there is chemical formula A
4group
table P: there is chemical formula A
4group
| Group | R 1 | R 2 | G 1 | G 2 | G 5 | G 4 |
| A5.001 | CH 3 | H | C-H | C-H | N | N |
| A5.002 | CF 3 | H | C-H | C-H | N | N |
| A5.003 | Cl | H | C-H | C-H | N | N |
| A5.004 | Br | H | C-H | C-H | N | N |
| A5.005 | CH 3 | H | C-H | N | N | N |
| A5.006 | CF 3 | H | C-H | N | N | N |
| A5.007 | Cl | H | C-H | N | N | N |
| A5.008 | Br | H | C-H | N | N | N |
| A5.009 | CH 3 | H | C-H | C-H | C-CH 3 | N |
| A5.010 | CF 3 | H | C-H | C-H | C-CH 3 | N |
| A5.011 | Cl | H | C-H | C-H | C-CH 3 | N |
| A5.012 | Br | H | C-H | C-H | C-CH 3 | N |
| A5.013 | CH 3 | H | C-H | N | C-CH 3 | N |
| A5.014 | CF 3 | H | C-H | N | C-CH 3 | N |
| A5.015 | Cl | H | C-H | N | C-CH 3 | N |
| A5.016 | Br | H | C-H | N | C-CH 3 | N |
table Q:there is chemical formula A
6group
table R:there is chemical formula A
7agroup
| Group | R 1 | G 1 | G 2 | G 3 |
| A7.001 | CH 3 | C-H | C-H | C-CH 3 |
| A7.002 | CF 3 | C-H | C-H | C-CH 3 |
| A7.003 | Cl | C-H | C-H | C-CH 3 |
| A7.004 | Br | C-H | C-H | C-CH 3 |
| A7.005 | CH 3 | C-H | C-H | C-H |
| A7.006 | CF 3 | C-H | C-H | C-H |
| A7.007 | Cl | C-H | C-H | C-H 111 --> |
| A7.008 | Br | C-H | C-H | C-H |
| A7.009 | CH 3 | C-H | C-H | N |
| A7.010 | CF 3 | C-H | C-H | N |
| A7.011 | Cl | C-H | C-H | N |
| A7.012 | Br | C-H | C-H | N |
table S:there is chemical formula A
8agroup
| Group | R 1 | G 1 | G 2 | G 4 |
| A8.001 | CH 3 | C-H | C-H | C-H |
| A8.002 | CF 3 | C-H | C-H | C-H |
| A8.003 | Cl | C-H | C-H | C-H |
| A8.004 | Br | C-H | C-H | C-H |
| A8.005 | CH 3 | C-H | C-H | C-CH 3 |
| A8.006 | CF 3 | C-H | C-H | C-CH 3 |
| A8.007 | Cl | C-H | C-H | C-CH 3 |
| A8.008 | Br | C-H | C-H | C-CH 3 |
| A8.009 | CH 3 | C-H | C-H | N |
| A8.010 | CF 3 | C-H | C-H | N |
| A8.011 | Cl | C-H | C-H | N |
| A8.012 | Br | C-H | C-H | N |
table 1:this table discloses the compound that 66 kinds have chemical formula A1.014-B1, and wherein group B 1 is the group B 1.049-B1.084 shown in Table A and B1.091-B1.120, and shows to define A1.014 in L.
table 2:this table discloses the compound that 66 kinds have chemical formula A1.018-B1, and wherein group B 1 is the group B 1.049-B1.084 shown in Table A and B1.091-B1.120, and shows to define A1.018 in L.
table 3:this table discloses the compound that 66 kinds have chemical formula A1.022-B1, and wherein group B 1 is the group B 1.049-B1.084 shown in Table A and B1.091-B1.120, and shows to define A1.022 in L.
table 4:this table discloses the compound that 36 kinds have chemical formula A1.014-B2, and wherein group B 2 is table group B 2.001-B2.036 shown in B, and shows to define A1.014 in L.
table 5:this table discloses the compound that 36 kinds have chemical formula A1.018-B2, and wherein group B 2 is table group B 2.001-B2.036 shown in B, and shows to define A1.018 in L.
table 6:this table discloses the compound that 36 kinds have chemical formula A1.022-B2, and wherein group B 2 is table group B 2.001-B2.036 shown in B, and shows to define A1.022 in L.
table 7:this table discloses the compound that 24 kinds have chemical formula A1.014-B3, and wherein group B 3 is table group B 3.001-B3.024 shown in C, and shows to define A1.014 in L.
table 8:this table discloses the compound that 24 kinds have chemical formula A1.018-B3, and wherein group B 3 is table group B 3.001-B3.024 shown in C, and shows to define A1.018 in L.
table 9:this table discloses the compound that 24 kinds have chemical formula A1.022-B3, and wherein group B 3 is table group B 3.001-B3.024 shown in C, and shows to define A1.022 in L.
table 10:this table discloses the compound that 8 kinds have chemical formula A1.014-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A1.014 in L.
table 11:this table discloses the compound that 8 kinds have chemical formula A1.018-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A1.018 in L.
table 12:this table discloses the compound that 8 kinds have chemical formula A1.022-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A1.022 in L.
table 13:this table discloses the compound that 24 kinds have chemical formula A1.014-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A1.014 in L.
table 14:this table discloses the compound that 24 kinds have chemical formula A1.018-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A1.018 in L.
table 15:this table discloses the compound that 24 kinds have chemical formula A1.022-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A1.022 in L.
table 16:this table discloses the compound that 16 kinds have chemical formula A1.014-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A1.014 in L.
table 17:this table discloses the compound that 16 kinds have chemical formula A1.018-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A1.018 in L.
table 18:this table discloses the compound that 16 kinds have chemical formula A1.022-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A1.022 in L.
table 19:this table discloses the compound that 54 kinds have chemical formula A1.014-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A1.014 in L.
table 20:this table discloses the compound that 54 kinds have chemical formula A1.018-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A1.018 in L.
table 21:this table discloses the compound that 54 kinds have chemical formula A1.022-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A1.022 in L.
table 22:this table discloses the compound that 12 kinds have chemical formula A1.014-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A1.014 in L.
table 23:this table discloses the compound that 12 kinds have chemical formula A1.018-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A1.018 in L.
table 24:this table discloses the compound that 12 kinds have chemical formula A1.022-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A1.022 in L.
table 25:this table discloses the compound that 30 kinds have chemical formula A1.014-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A1.014 in L.
table 26:this table discloses the compound that 30 kinds have chemical formula A1.018-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A1.018 in L.
table 27:this table discloses the compound that 30 kinds have chemical formula A1.022-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A1.0122 in L.
table 28:this table discloses the compound that 12 kinds have chemical formula A1.014-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A1.014 in L.
table 29:this table discloses the compound that 12 kinds have chemical formula A1.018-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A1.018 in L.
table 30:this table discloses the compound that 12 kinds have chemical formula A1.022-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A1.022 in L.
table 31:this table discloses the compound that 64 kinds have chemical formula A1.014-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A1.014 in L.
table 29:this table discloses the compound that 64 kinds have chemical formula A1.018-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A1.018 in L.
table 30:this table discloses the compound that 64 kinds have chemical formula A1.022-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A1.022 in L.
table 31:this table discloses the compound that 132 kinds have chemical formula A2.006-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A2.006 in M.
table 32:this table discloses the compound that 132 kinds have chemical formula A2.018-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A2.018 in M.
table 33:this table discloses the compound that 36 kinds have chemical formula A2.006-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A2.006 in M.
table 34:this table discloses the compound that 36 kinds have chemical formula A2.018-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A2.018 in M.
table 35:this table discloses the compound that 24 kinds have chemical formula A2.006-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A2.0006 in M.
table 36:this table discloses the compound that 24 kinds have chemical formula A2.018-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A2.018 in M.
table 37:this table discloses the compound that 8 kinds have chemical formula A2.006-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A2.006 in M.
table 38:this table discloses the compound that 8 kinds have chemical formula A2.018-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A2.018 in M.
table 39:this table discloses the compound that 24 kinds have chemical formula A2.006-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A2.006 in M.
table 40:this table discloses the compound that 24 kinds have chemical formula A2.018-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A2.018 in M.
table 42:this table discloses the compound that 16 kinds have chemical formula A2.006-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A2.006 in M.
table 43:this table discloses the compound that 16 kinds have chemical formula A2.018-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A2.018 in M.
table 44:this table discloses the compound that 54 kinds have chemical formula A2.006-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A2.0106 in M.
table 45:this table discloses the compound that 54 kinds have chemical formula A2.018-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A2.018 in M.
table 46:this table discloses the compound that 12 kinds have chemical formula A2.006-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A2.006 in M.
table 47:this table discloses the compound that 12 kinds have chemical formula A2.018-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A2.018 in M.
table 48:this table discloses the compound that 30 kinds have chemical formula A2.006-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A2.006 in M.
table 49:this table discloses the compound that 30 kinds have chemical formula A2.018-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A2.018 in M.
table 50:this table discloses the compound that 12 kinds have chemical formula A2.006-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A2.006 in M.
table 51:this table discloses the compound that 12 kinds have chemical formula A2.018-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A2.018 in M.
table 52:this table discloses the compound that 64 kinds have chemical formula A2.006-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A2.006 in M.
table 53:this table discloses the compound that 64 kinds have chemical formula A2.018-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A2.018 in M.
table 54:this table discloses the compound that 132 kinds have chemical formula A3.006-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A3.006 in N.
table 55:this table discloses the compound that 132 kinds have chemical formula A3.018-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A3.018 in N.
table 56:this table discloses the compound that 36 kinds have chemical formula A3.006-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A3.006 in N.
table 57:this table discloses the compound that 36 kinds have chemical formula A3.018-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A3.018 in N.
table 58:this table discloses the compound that 24 kinds have chemical formula A3.006-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A3.006 in N.
table 59:this table discloses the compound that 24 kinds have chemical formula A3.018-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A3.018 in N.
table 60:this table discloses the compound that 8 kinds have chemical formula A3.006-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A3.006 in N.
table 61:this table discloses the compound that 8 kinds have chemical formula A3.018-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A3.018 in N.
table 62:this table discloses the compound that 24 kinds have chemical formula A3.006-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A3.006 in N.
table 63:this table discloses the compound that 24 kinds have chemical formula A3.018-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A3.018 in N.
table 64:this table discloses the compound that 16 kinds have chemical formula A3.006-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A3.006 in N.
table 65:this table discloses the compound that 16 kinds have chemical formula A3.018-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A3.018 in N.
table 66:this table discloses the compound that 54 kinds have chemical formula A3.006-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A3.006 in N.
table 67:this table discloses the compound that 54 kinds have chemical formula A3.018-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A3.018 in N.
table 68:this table discloses the compound that 12 kinds have chemical formula A3.006-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A3.006 in N.
table 69:this table discloses the compound that 12 kinds have chemical formula A3.0018-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A3.018 in N.
table 70:this table discloses the compound that 30 kinds have chemical formula A3.006-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A3.006 in N.
table 71:this table discloses the compound that 30 kinds have chemical formula A3.018-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A3.018 in N.
table 72:this table discloses the compound that 12 kinds have chemical formula A3.006-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A3.006 in N.
table 73:this table discloses the compound that 12 kinds have chemical formula A3.018-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A3.018 in N.
table 74:this table discloses the compound that 64 kinds have chemical formula A3.006-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A3.006 in N.
table 75:this table discloses the compound that 64 kinds have chemical formula A3.018-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A3.018 in N.
table 76:this table discloses the compound that 132 kinds have chemical formula A4.006-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A4.006 in O.
table 77:this table discloses the compound that 132 kinds have chemical formula A4.008-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A4.008 in O.
table 78:this table discloses the compound that 36 kinds have chemical formula A4.006-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A4.006 in O.
table 79:this table discloses the compound that 36 kinds have chemical formula A4.008-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A4.008 in O.
table 80:this table discloses the compound that 24 kinds have chemical formula A4.006-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A4.006 in O.
table 81:this table discloses the compound that 24 kinds have chemical formula A4.008-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A4.008 in O.
table 82:this table discloses the compound that 8 kinds have chemical formula A4.006-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A4.006 in O.
table 83:this table discloses the compound that 8 kinds have chemical formula A4.008-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A4.008 in O.
table 84:this table discloses the compound that 24 kinds have chemical formula A4.006-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A4.006 in O.
table 85:this table discloses the compound that 24 kinds have chemical formula A4.008-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A4.008 in O.
table 86:this table discloses the compound that 16 kinds have chemical formula A4.006-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A4.006 in O.
table 87:this table discloses the compound that 16 kinds have chemical formula A4.008-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A4.008 in O.
table 88:this table discloses the compound that 54 kinds have chemical formula A4.006-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A4.006 in O.
table 89:this table discloses the compound that 54 kinds have chemical formula A4.008-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A4.008 in O.
table 90:this table discloses the compound that 12 kinds have chemical formula A4.006-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A4.006 in O.
table 91:this table discloses the compound that 12 kinds have chemical formula A4.008-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A4.008 in O.
table 92:this table discloses the compound that 30 kinds have chemical formula A4.006-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A4.006 in O.
table 93:this table discloses the compound that 30 kinds have chemical formula A4.008-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A4.008 in O.
table 94:this table discloses the compound that 12 kinds have chemical formula A4.006-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A4.006 in O.
table 95:this table discloses the compound that 12 kinds have chemical formula A4.008-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A4.008 in O.
table 96:this table discloses the compound that 64 kinds have chemical formula A4.006-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A4.006 in O.
table 97:this table discloses the compound that 64 kinds have chemical formula A4.008-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A3.008 in O.
table 98:this table discloses the compound that 132 kinds have chemical formula A5.006-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A5.006 in P.
table 99:this table discloses the compound that 36 kinds have chemical formula A5.006-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A5.006 in P.
table 100:this table discloses the compound that 24 kinds have chemical formula A5.006-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A5.006 in P.
table 101:this table discloses the compound that 8 kinds have chemical formula A5.006-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A4.006 in P.
table 102:this table discloses the compound that 24 kinds have chemical formula A5.006-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A5.006 in P.
table 103:this table discloses the compound that 16 kinds have chemical formula A5.006-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A5.006 in P.
table 104:this table discloses the compound that 54 kinds have chemical formula A5.006-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A5.006 in P.
table 105:this table discloses the compound that 12 kinds have chemical formula A5.006-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A5.006 in P.
table 106:this table discloses the compound that 30 kinds have chemical formula A5.006-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A5.006 in P.
table 107:this table discloses the compound that 12 kinds have chemical formula A5.006-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A5.006 in P.
table 108:this table discloses the compound that 64 kinds have chemical formula A5.006-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A5.006 in P.
table 109:this table discloses the compound that 132 kinds have chemical formula A6.002-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A6.002 in Q.
table 110:this table discloses the compound that 132 kinds have chemical formula A6.014-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A6.014 in Q.
table 111:this table discloses the compound that 36 kinds have chemical formula A6.002-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A6.002 in Q.
table 112:this table discloses the compound that 36 kinds have chemical formula A6.014-B2, and wherein group B 2 is table group B 2.001-B2.0036 shown in B, and shows to define A6.014 in Q.
table 113:this table discloses the compound that 24 kinds have chemical formula A6.002-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A6.002 in Q.
table 114:this table discloses the compound that 24 kinds have chemical formula A6.014-B3, and wherein group B 3 is table group B 3.001-B3.0024 shown in C, and shows to define A6.014 in Q.
table 115:this table discloses the compound that 8 kinds have chemical formula A6.002-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A6.002 in Q.
table 116:this table discloses the compound that 8 kinds have chemical formula A6.014-B4, and wherein group B 4 is table group B 4.001-B4.008 shown in D, and shows to define A6.014 in Q.
table 117:this table discloses the compound that 24 kinds have chemical formula A6.002-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A6.002 in Q.
table 118:this table discloses the compound that 24 kinds have chemical formula A6.014-B5, and wherein group B 5 is table group B 5.001-B5.024 shown in E, and shows to define A4.014 in Q.
table 119:this table discloses the compound that 16 kinds have chemical formula A6.002-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A6.002 in Q.
table 120:this table discloses the compound that 16 kinds have chemical formula A6.014-B6, and wherein group B 6 is table group B 6.001-B6.016 shown in F, and shows to define A6.014 in Q.
table 121:this table discloses the compound that 54 kinds have chemical formula A6.002-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A6.002 in Q.
table 122:this table discloses the compound that 54 kinds have chemical formula A6.014-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A6.014 in Q.
table 123:this table discloses the compound that 12 kinds have chemical formula A6.002-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A6.002 in Q.
table 124:this table discloses the compound that 12 kinds have chemical formula A6.0014-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A6.014 in Q.
table 125:this table discloses the compound that 30 kinds have chemical formula A6.002-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A6.002 in Q.
table 126:this table discloses the compound that 30 kinds have chemical formula A6.014-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A6.014 in Q.
table 127:this table discloses the compound that 12 kinds have chemical formula A6.002-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A6.002 in Q.
table 128:this table discloses the compound that 12 kinds have chemical formula A6.014-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A6.014 in Q.
table 129:this table discloses the compound that 64 kinds have chemical formula A6.002-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A6.002 in Q.
table 130:this table discloses the compound that 64 kinds have chemical formula A6.014-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A6.014 in Q.
table 131: this table discloses the compound that 132 kinds have chemical formula A7.002-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A7.002 in R.
table 132:this table discloses the compound that 132 kinds have chemical formula A7.006-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A7.006 in R.
table 133:this table discloses the compound that 132 kinds have chemical formula A7.010-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A7.010 in R.
table 134:this table discloses the compound that 54 kinds have chemical formula A7.002-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A7.002 in R.
table 135:this table discloses the compound that 54 kinds have chemical formula A7.006-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A7.006 in R.
table 136:this table discloses the compound that 54 kinds have chemical formula A7.010-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A7.010 in R.
table 137:this table discloses the compound that 12 kinds have chemical formula A7.002-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A7.002 in R.
table 138:this table discloses the compound that 12 kinds have chemical formula A7.006-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A7.006 in R.
table 139:this table discloses the compound that 12 kinds have chemical formula A7.010-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A7.010 in R.
table 140:this table discloses the compound that 30 kinds have chemical formula A7.002-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A7.002 in R.
table 142:this table discloses the compound that 30 kinds have chemical formula A7.006-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A7.006 in R.
table 143:this table discloses the compound that 30 kinds have chemical formula A7.010-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A7.010 in R.
table 144:this table discloses the compound that 12 kinds have chemical formula A7.002-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A7.002 in R.
table 145:this table discloses the compound that 12 kinds have chemical formula A7.006-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A7.006 in R.
table 146:this table discloses the compound that 12 kinds have chemical formula A7.010-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A7.010 in R.
table 147:this table discloses the compound that 64 kinds have chemical formula A7.002-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A7.002 in R.
table 148:this table discloses the compound that 64 kinds have chemical formula A7.006-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A7.006 in R.
table 149:this table discloses the compound that 64 kinds have chemical formula A7.010-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A7.010 in R.
table 150: this table discloses the compound that 132 kinds have chemical formula A8.002-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A8.002 in R.
table 151:this table discloses the compound that 132 kinds have chemical formula A8.006-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A8.006 in S.
table 152:this table discloses the compound that 132 kinds have chemical formula A8.010-B1, and wherein group B 1 is the group B 1.001-B1.132 shown in Table A, and shows to define A8.010 in S.
table 153:this table discloses the compound that 54 kinds have chemical formula A8.002-B7, and wherein group B 7 is table group B 7.001-B7.054 shown in G, and shows to define A8.002 in S.
table 154:this table discloses the compound that 54 kinds have chemical formula A8.006-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A8.006 in R.
table 155:this table discloses the compound that 54 kinds have chemical formula A8.010-B7, and wherein B7 is the group B 7.001-B7.054 of table shown in G, and shows to define A8.010 in R.
table 156:this table discloses the compound that 12 kinds have chemical formula A8.002-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A8.002 in S.
table 157:this table discloses the compound that 12 kinds have chemical formula A8.006-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A8.006 in S.
table 158:this table discloses the compound that 12 kinds have chemical formula A8.010-B8, and wherein group B 8 is table group B 8.001-B8.012 shown in H, and shows to define A8.010 in S.
table 159:this table discloses the compound that 30 kinds have chemical formula A8.002-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A8.002 in S.
table 160:this table discloses the compound that 30 kinds have chemical formula A4.006-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A8.006 in S.
table 161:this table discloses the compound that 30 kinds have chemical formula A8.010-B9, and wherein group B 9 is the group B 9.001-B9.030 shown in Table I, and shows to define A8.010 in S.
table 162:this table discloses the compound that 12 kinds have chemical formula A8.002-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A8.002 in S.
table 164:this table discloses the compound that 12 kinds have chemical formula A8.006-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A8.006 in S.
table 165:this table discloses the compound that 12 kinds have chemical formula A8.010-B10, and wherein group B 10 is table group B 10.001-B10.012 shown in J, and shows to define A8.010 in S.
table 166:this table discloses the compound that 64 kinds have chemical formula A8.002-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A8.002 in S.
table 167:this table discloses the compound that 64 kinds have chemical formula A8.006-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A8.006 in S.
table 168:this table discloses the compound that 64 kinds have chemical formula A8.010-B11, and wherein group B 11 is table group B 11.001-B11.064 shown in K, and shows to define A8.010 in S.
table T: the physicochemical data with the compound of Formula I:
table U: especially preferred have the compound of Formula I and the physicochemical data of intermediate thereof:
Preferably provide the compound that a group has Formula I, the embodiment illustrated as following (1) to (7) define:
One group of especially preferred compound with Formula I according to the present invention as embodiment (1) define, and comprise following combination
(1): group A2 and group B, B is selected from B7, B9 and B11;
Wherein A2 is preferably represented by group A2.1
Wherein R
40halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
G
21nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And
G
51nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And group B 7, B9 and B11 are preferably represented by the group being selected from B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Especially preferred compound according to embodiment (1) is represented by embodiment (1.1), wherein
(1.1), in group A2.1
R
40c
1-C
4haloalkyl, particularly trifluoromethyl;
G
21nitrogen or CH; And
G
51nitrogen or C-C
1-C
6alkyl, particularly nitrogen or C-methyl;
And in group B 7.1, B9.1 and B11.1
M is 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, preferred ethyl; And
R
42c
1-C
4haloalkyl, preferred trifluoromethyl;
M is 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, preferred ethyl; And
R
44c
1-C
4haloalkyl, preferred trifluoromethyl;
M is 2;
R
45c
1-C
4alkyl, preferred ethyl; And
R
46c
1-C
4haloalkyl, preferred trifluoromethyl.
According to the especially preferred compound with Formula I of another group according to the present invention as embodiment (2) define, and comprise following combination
(2): group A3 and group B, B is selected from B7, B9 and B11;
Wherein A3 is preferably represented by group A3.1
Wherein R
47halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
G
41nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And
G
22nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And group B 7, B9 and B11 are preferably represented by the group being selected from B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Especially preferred compound according to embodiment (2) is represented by embodiment (2.1), wherein
(2.1), in group A3.1
R
47c
1-C
4haloalkyl, particularly trifluoromethyl;
G
22nitrogen or CH; And
G
41nitrogen or C-C
1-C
6alkyl, particularly nitrogen or C-methyl;
And in group B 7.1, B9.1 and B11.1
M is 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, preferred ethyl; And
R
42c
1-C
4haloalkyl, preferred trifluoromethyl;
M is 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, preferred ethyl; And
R
44c
1-C
4haloalkyl, preferred trifluoromethyl;
M is 2;
R
45c
1-C
4alkyl, preferred ethyl; And
R
46c
1-C
4haloalkyl, preferred trifluoromethyl.
According to the especially preferred compound with Formula I of another group according to the present invention as embodiment (3) define, and comprise following combination
(3): group A4 and group B 1;
Wherein A4 is preferably represented by group A4.1
Wherein R
48halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
J
3sulphur oxygen or N-methyl; And
R
49hydrogen, C
1-C
6alkyl, C
1-C
6haloalkyl, halogen, CN, O-C
1-C
4alkyl, S-C
1-C
4alkyl, SO
2-C
1-C
4alkyl, S-phenyl, SO
2-phenyl or SO
2-C
1-C
4haloalkyl;
And group B 1 is
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Preferred compound according to embodiment (3) is also represented by embodiment (3.1), wherein
(3.1), in group A4.1
R
48c
1-C
4haloalkyl, particularly trifluoromethyl;
J
3oxygen, sulphur or N-methyl; And
G
49hydrogen or C
1-C
6alkyl, particularly hydrogen or methyl;
And group B 1, B7, B9 and B11 are preferably represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Other especially preferred compound according to embodiment (3) is represented by embodiment (3.2), wherein (3.2), in group A4.1
R
48c
1-C
4haloalkyl, particularly trifluoromethyl;
J
3oxygen, sulphur or N-methyl; And
G
49hydrogen or C
1-C
6alkyl, particularly hydrogen or methyl;
And in group B 1.1
M is 2;
V
11nitrogen or methyne;
R
51c
1-C
4alkyl, preferred ethyl; And
R
50hydrogen or C
1-C
4haloalkyl, preferred hydrogen or trifluoromethyl.
According to the especially preferred compound with Formula I of another group according to the present invention as embodiment (4) define, and comprise following combination
(4): group A5 and group B, B is selected from B1, B7, B9 and B11;
Wherein A5 is preferably represented by group A5.1
Wherein
G
55nitrogen or C-R
53;
R
53c
1-C
4alkyl;
G
25nitrogen or methyne; And
R
52halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are preferably represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Especially preferred compound according to embodiment (4) is represented by embodiment (4.1), wherein
(4.1), in group A5.1
R
52c
1-C
4haloalkyl, particularly trifluoromethyl;
G
55nitrogen or C-C
1-C
4alkyl, preferred nitrogen or methyl; And
G
25nitrogen or methyne;
And in group B 1.1
M is 2;
V
11nitrogen or methyne;
R
51c
1-C
4alkyl, preferred ethyl; And
R
50hydrogen or C
1-C
4haloalkyl, preferred hydrogen or trifluoromethyl;
In group B 7.1
M is 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, preferred ethyl; And
R
42c
1-C
4haloalkyl, preferred trifluoromethyl;
In group B 9.1
M is 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, preferred ethyl; And
R
44c
1-C
4haloalkyl, preferred trifluoromethyl;
And in group B 11.1
M is 2;
R
45c
1-C
4alkyl, preferred ethyl; And
R
46c
1-C
4haloalkyl, preferred trifluoromethyl.
According to the particularly preferred compound with Formula I of another group according to the present invention as embodiment (5) define, and comprise following combination
(5): group A6 and group B, B is selected from B1, B7, B9 and B11;
Wherein A6 is preferably represented by group A6.1
Wherein
G
36n-R
55, oxygen or sulphur;
R
55c
1-C
4alkyl;
G
26nitrogen or methyne; And
R
54halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are preferably represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
Nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Especially preferred compound according to embodiment (5) is represented by embodiment (5.1), wherein
(5.1), in group A6.1
R
54c
1-C
4haloalkyl, particularly trifluoromethyl;
G
36n-C
1-C
4alkyl, oxygen or sulphur; Preferred N-CH
3, oxygen or sulphur; And
G
26nitrogen or methyne;
And in group B 1.1
M is 2;
V
11nitrogen or methyne;
R
51c
1-C
4alkyl, preferred ethyl; And
R
50hydrogen or C
1-C
4haloalkyl, preferred hydrogen or trifluoromethyl;
In group B 7.1
M is 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, preferred ethyl; And
R
42c
1-C
4haloalkyl, preferred trifluoromethyl;
In group B 9.1
M is 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, preferred ethyl; And
R
44c
1-C
4haloalkyl, preferred trifluoromethyl;
And in group B 11.1
M is 2;
R
45c
1-C
4alkyl, preferred ethyl; And
R
46c
1-C
4haloalkyl, preferred trifluoromethyl.
According to the especially preferred compound with Formula I of another group according to the present invention as embodiment (6) define, and comprise following combination
(6): group A7 and group B, B is selected from B1, B7, B9 and B11;
Wherein A7 is preferably represented by group A7.1
Wherein
G
57nitrogen or C-R
57;
R
57hydrogen or C
1-C
4alkyl; And
R
56halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are preferably represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82it is nitrogen methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Especially preferred compound according to embodiment (6) is represented by embodiment (6.1), wherein
(6.1), in group A7.1
R
56c
1-C
4haloalkyl, particularly trifluoromethyl; And
G
57nitrogen, C-H or C-C
1-C
4alkyl; Preferred nitrogen, C-H or C-CH
3;
And in group B 1.1
M is 2;
V
11nitrogen or methyne;
R
51c
1-C
4alkyl, preferred ethyl; And
R
50hydrogen or C
1-C
4haloalkyl, preferred hydrogen or trifluoromethyl;
In group B 7.1
M is 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, preferred ethyl; And
R
42c
1-C
4haloalkyl, preferred trifluoromethyl;
In group B 9.1
M is 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, preferred ethyl; And
R
44c
1-C
4haloalkyl, preferred trifluoromethyl;
And in group B 11.1
M is 2;
R
45c
1-C
4alkyl, preferred ethyl; And
R
46c
1-C
4haloalkyl, preferred trifluoromethyl.
According to the especially preferred compound with Formula I of another group according to the present invention as embodiment (7) define, and comprise following combination
(7): group A8 and group B, B is selected from B1, B7, B9 and B11;
Wherein A8 is preferably represented by group A8.1
Wherein
G
48nitrogen or C-R
59;
R
59hydrogen or C
1-C
4alkyl; And
R
58halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are preferably represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
Especially preferred compound according to embodiment (7) is represented by embodiment (7.1), wherein
(7.1), in group A8.1
R
58c
1-C
4haloalkyl, particularly trifluoromethyl; And
G
48nitrogen, C-H or C-C
1-C
4alkyl; Preferred nitrogen, C-H or C-CH
3;
And in group B 1.1
M is 2;
V
11nitrogen or methyne;
R
51c
1-C
4alkyl, preferred ethyl; And
R
50hydrogen or C
1-C
4haloalkyl, preferred hydrogen or trifluoromethyl;
In group B 7.1
M is 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, preferred ethyl; And
R
42c
1-C
4haloalkyl, preferred trifluoromethyl;
In group B 9.1
M is 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, preferred ethyl; And
R
44c
1-C
4haloalkyl, preferred trifluoromethyl;
And in group B 11.1
M is 2;
R
45c
1-C
4alkyl, preferred ethyl; And
R
46c
1-C
4haloalkyl, preferred trifluoromethyl.
The especially preferred compound with Formula I of the present invention is listed in following Table V 1 to V26.Table V 1 to V26 represents other embodiment of the present invention: in these tables, Et is CH
2cH
3, Me is CH
3, NMe is N-CH3, CMe is C-Me etc.
table V 1: the compound with chemical formula A2.1-B7.1:
table V 2: the compound with chemical formula A2.1-B9.1:
table V 3: the compound with chemical formula A2.1-B11.1:
table V 4: the compound with chemical formula A3.1-B7.1:
tablev
5: the compound with chemical formula A3.1-B9.1:
tablev
6: the compound with chemical formula A3.1-B11.1:
table V 7: the compound with chemical formula A4.1-B1.1:
table V 8: the compound with chemical formula A5.1-B1.1:
table V 9: the compound with chemical formula A5.1-B7.1:
table V 10: the compound with chemical formula A5.1-B9.1:
tablev
11: the compound with chemical formula A5.1-B11.1:
table V 12: the compound with chemical formula A6.1-B1.1:
table V 13: the compound with chemical formula A6.1-B7.1:
table V 14: the compound with chemical formula A6.1-B9.1:
table V 15: the compound with chemical formula A6.1-B11.1:
table V 16: the compound with chemical formula A7.1-B1.1:
table V 17: the compound with chemical formula A7.1-B7.1:
table V 18: the compound with chemical formula A7.1-B9.1:
table V 19: the compound with chemical formula A7.1-B11.1:
table V 20: the compound with chemical formula A8.1-B1.1:
table V 21: the compound with chemical formula A8.1-B7.1:
table V 22: the compound with chemical formula A8.1-B9.1:
tablev
23: the compound with chemical formula A8.1-B11.1:
table V 24: the compound with chemical formula A4.1-B7.1:
table V 25: the compound with chemical formula A4.1-B9.1:
table V 26: the compound with chemical formula A4.1-B11.1:
Preparation example (%=weight percent)
The emulsion of any desired concentration can be prepared from these enriched materials by dilute with water.
These solution are applicable to using with the form of droplet.
By this solubilize active ingredients in methylene dichloride, solvent is evaporated on one or more carriers by this solution spray subsequently under vacuo.
The agent of instant dirt is obtained by carrier and activeconstituents closely being mixed.
Activeconstituents is mixed with additive and grind this mixture fully in a suitable shredder.These give wettable powder, these wettable powders can carry out diluting with water the suspension providing arbitrary desired concentration.
example F6: forcing machine particle
Mixed with these additives by this activeconstituents, and grind this mixture, moistening with water, extruding, granulation is also dry in the air stream.
example F7: the particle of dressing
Activeconstituents 3%
Polyoxyethylene glycol (MW200) 3%
Kaolin 94%
In a mixing tank, the activeconstituents of this fine grinding is administered on the kaolin having used polyoxyethylene glycol moistening equably.These give dustless coated granule.
example F8: suspension-concentrates
The activeconstituents of this fine grinding is mixed closely with these additives.Anyly wish that the suspension of concentration can be prepared from the suspension-concentrates obtained like this by dilute with water.
This combination fully mixed with these adjuvants and mixture is fully ground in a suitable shredder, thus obtaining the powder that can be directly used in seed treatment.
example F10: emulsifiable concentrate
In plant protection, the operable emulsion with any required dilution can be obtained from this enriched material by dilute with water.
example F11: for the flowed enriched material of seed treatment
The combination of this fine dispersion is closely mixed with these adjuvants, thus gives a kind of suspension-concentrates, dilute with water can be made to obtain any desired suspension from this enriched material.Use this type of dilution body, can to process together with plant propagation material the plant lived and to its for microbial infection by spraying, toppling over or flood and protect.
Have by adding other composition killing insect, kill mite and/or Fungicidally active, the activity according to these compositions of the present invention can be widened significantly, and is suitable for environment at that time.Have the compound of Formula I and other have kill insect, the mixture of the composition that kills mite and/or Fungicidally active can also have further, unexpected advantage, these advantages can also be described as synergistic activity in wider implication.Such as, plant is to the phytotoxicity of its better tolerance, reduction, insect can be controlled or in their production period (such as, in grinding or mixing process, in their storage or their use procedure) better behavior in their different developmental phases.
Here; the additive of suitable activeconstituents is; such as, the representative of the activeconstituents of classification below: organo phosphorous compounds, nitrophenol derivative, thiocarbamide, neotonin, carbonamidine, benzophenone derivates, ureas, pyrrole derivative, carbamate, pyrethroid, chlorinated hydrocarbon, acylurea, pyridylmethylene amino derivative, Macrolide, neonicotine and sporeine preparation.
The mixture of the compound and activeconstituents below with Formula I is preferred (abridge " TX " means " be selected from a kind of compound of lower group, this group forms to the compound in 168 and V1 to V26 by being described in table 1 of the present invention "):
A kind of adjuvant, this adjuvant is selected from the group be made up of following material: oil (substituting title (628)+TX),
A kind of miticide, this miticide is selected from the group be made up of following material: acequinocyl ([57960-19-7] [CCN])+TX, fenpyroximate [134098-61-6] [CCN]+TX, fluoro-Cyano chrysanthemate [70124-77-5] [CCN]+TX, 1,1-bis-(4-chloro-phenyl-)-cellosolvo (IUPAC title) (910)+TX, hexythiazox [78587-05-0] [CCN]+TX, 2,4 dichloro benzene base benzene sulfonate (IUPAC/ chemical abstracts name) (1059)+TX, the fluoro-N-methyl of 2--N-1-naphthalene acetamide (IUPAC title) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC title) (981)+TX, Avrmectin (1)+TX, acequinocyl (3)+TX, acetyl worm nitrile [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, α-Cypermethrin (202)+TX, amidithion (870)+TX, sulfanilamide (SN) mite ester [CCN]+TX, aminothio salt (872)+TX, Tetram (875)+TX, Tetram binoxalate (875)+TX, amitraz (24)+TX, aramite (881)+TX, white arsenic (882)+TX, AVI382 (compound code)+TX, AZ60541 (compound code)+TX, azinphos_ethyl (44)+TX, R-1582 (azinphos-methyl) (45)+TX, nitrogen benzide (IUPAC title) (888)+TX, azocyclotin (46)+TX, Alamos (889)+TX, benzene mattress spirit (62)+TX, the husky phosphorus (benoxafos) of benzene promise (substituting title) [CCN]+TX, benzoximate (71)+TX, peruscabin (IUPAC title) [CCN]+TX, Bifenazate (74)+TX, bifenthrin (76)+TX, Niagara 9044 (907)+TX, brofenvalerate (substituting title)+TX, bromocyclne (bromocyclen) (918)+TX, bromofos (920)+TX, bromophos_ethyl (921)+TX, bromopropylate (94)+TX, Buprofezin (99)+TX, butocarboxim (103)+TX, butanone sulfone prestige (104)+TX, butocarboxim (butylpyridaben) (substituting title)+TX, lime sulfur mixture (IUPAC title) (111)+TX, toxaphene (941)+TX, sok (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, Carbophenothion (947)+TX, CGA50 ' 439 (research code) (125)+TX, chinomethionate (chinomethionat) (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeform-hydrochloride (964)+TX, bromothalonil (130)+TX, chlorfenethol (968)+TX, Ovotran (970)+TX, chlorfensulphide (971)+TX, Clofenvinfos (131)+TX, G-23922 (975)+TX, Yi Tuoming (chloromebuform) (977)+TX, chloromethiuron (978)+TX, chloropropylate (983)+TX, Chlorpyrifos 94 (145)+TX, chlorpyrifos_methyl (146)+TX, pirimiphosmethyl (994)+TX, cinerin (696)+TX, cinerin 11 (696)+TX, II cinerin II (cinerins) (696)+TX, clofentezine (158)+TX, closantel (substituting title) [CCN]+TX, Coumaphos (174)+TX, crotamiton (substituting title) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate (1020)+TX, cyflumetofen [400882-07-7]+TX, three cyhalothrins (196)+TX, cyhexatin (199)+TX, Cypermethrin (201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion demephion_O demephion (1037)+TX, demephion demephion_O demephion-O (1037)+TX, demephion demephion_O demephion-S (1037)+TX, Systox (1038)+TX, demeton_S_methyl (224)+TX, Systox-O (1038)+TX, demeton_S_methyl-O (224)+TX, Systox-S (1038)+TX, demeton_S_methyl-S (224)+TX, Systox-S-methyl sulphur grand (demeton-S-methylsulphon) (1039)+TX, methamidophos (226)+TX, dialifos (1042)+TX, diazinon (227)+TX, dichlofluanid (230)+TX, SD-1750 (236)+TX, tetramethyldiamidophosphoric fluoride (dicliphos) (substituting title)+TX, Mitigan (242)+TX, Carbicron (243)+TX, gram (1071)+TX everywhere, tetramethyldiamidophosphoric fluoride (dimefox) (1081)+TX, Rogor (262)+TX, diformazan polynactin (dinactin) (substituting title) (653)+TX, dinex (dinex) (1089)+TX, dinex (dinex-diclexine) (1089)+TX, dinobuton (dinobuton) (269)+TX, dinocap (dinocap) (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX, dinitro ester (1090)+TX, dinopenton (dinopenton) (1092)+TX, nitre monooctyl ester (1097)+TX, dinoterbon (1098)+TX, Kavadel (1102)+TX, sulfobenzide (IUPAC title) (1103)+TX, Tosse) (substituting title) [CCN]+TX, thiodemeton (278)+TX, DNOC (282)+TX, benzene oxycetylene mite (dofenapyn) (1113)+TX, doramectin (substituting title) [CCN]+TX, 5a,6,9,9a-hexahydro-6,9-methano-2,4 (294)+TX, endothion (1121)+TX, EPN (297)+TX, Eprinomectin (substituting title) [CCN]+TX, Nialate (309)+TX, ethoate_methyl (ethoate-methyl) (1134)+TX, second mite azoles (320)+TX, etrimfos (1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX, fenothiocarb (337)+TX, Fenvalerate (342)+TX, tebufenpyrad (fenpyrad) (substituting title)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fluorine nitre pentanoic (fentrifanil) (1161)+TX, fenvalerate (349)+TX, ethiprole (354)+TX, Fluacrypyrim (360)+TX, fluazuron (1166)+TX, fluorine mite thiophene (1167)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, Fluenyl (1169)+TX, flufenoxuron (370)+TX, flumethrin (372)+TX, fluoraracide (1174)+TX, taufluvalinate (1184)+TX, FMC1137 (research code) (1185)+TX, anti-mite amidine (405)+TX, anti-mite amidine hydrochloride (405)+TX, formothion (1192)+TX, amine first prestige (formparanate) (1193)+TX, Xiang-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptene ether (432)+TX, hexadecane basic ring carboxylate (IUPAC/ chemical abstracts name) (1216)+TX, hexythiazox (441)+TX, methyl iodide (IUPAC title) (542)+TX, isocarbophos (substituting title) (473)+TX, sec.-propyl 0-(Methoxyamino thiophosphoryl) salicylate (IUPAC title) (473)+TX, ivermectin (substituting title) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, iodfenphos TOP (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, Malathion (492)+TX, benzyl propane dinitrile (malonoben) (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, Sudermo (substituting title) [CCN]+TX, methacrifos (1266)+TX, acephatemet (527)+TX, methidathion (529)+TX, metmercapturon (530)+TX, methomyl (531)+TX, monobromethane (537)+TX, meta-tolyl-N-methylcarbamate (MTMC) (550)+TX, Phosdrin (556)+TX, Mexacarbate (1290)+TX, milbemycin (557)+TX, kill mite mattress element oxime (substituting title) [CCN]+TX, mipafox (1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, Moxidectin (substituting title) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-152 (compound code)+TX, fluorine mosquito spirit (1309)+TX, nikkomycin (substituting title) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex compound (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, omethoate (omethoate) (594)+TX, oxamyl (602)+TX, sub-Thiometan (oxydeprofos) (1324)+TX, oxydisulfoton (1325)+TX, pp '-DDT (219)+TX, thiophos (615)+TX, permethrin (626)+TX, oil (substituting title) (628)+TX, phenkapton (1330)+TX, Tsidial (631)+TX, phorate (636)+TX, Phosalone (637)+TX, phosfolan (1338)+TX, R-1504 (638)+TX, phosphamidon (639)+TX, Volaton (642)+TX, pririmiphos_methyl (652)+TX, Terpene polychlorinates (polychloroterpenes) (traditional title) (1347)+TX, polynactin (polynactins) (substituting title) (653)+TX, R 8284 (1350)+TX, Profenofos (662)+TX, promacyl (1354)+TX, propargite (671)+TX, propetamphos (673)+TX, Propoxur (678)+TX, prothidathion (1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, chrysanthemumdicarboxylic acid monomethyl ester pyrethrolone ester (696)+TX, pyrethrin (696)+TX, pyridaben (699)+TX, pyridaphenthione (701)+TX, pyrimidifen (706)+TX, Pyrimitate (1370)+TX, Resitox (711)+TX, Resitox (1381)+TX, R-1492 (research code) (1382)+TX, RA-17 (research code) (1383)+TX, tubatoxin (722)+TX, schradan (1389)+TX, cadusafos (sebufos) (substituting title)+TX, plug draws rhzomorph (substituting title) [CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX, Spiromesifen (739)+TX, SSI-121 (research code) (1404)+TX, Sulfiram (substituting title) [CCN]+TX, sulfluramid (750)+TX, sulfotep (753)+TX, Sulfur (754)+TX, S21-121 (research code) (757)+TX, taufluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam (substituting title)+TX, Tetrachlorvinphos (777)+TX, tetradifon (786)+TX, polynactin (substituting title) (653)+TX, kill mite thioether (tetrasul) (1425)+TX, thiofanox (thiafenox) (substituting title)+TX, Talcord (1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX, Su Li rhzomorph (thuringiensin) (substituting title) [CCN]+TX, prestige mattress phosphorus (1441)+TX, benzene thiophene mite (1443)+TX, triazophos (820)+TX, azoles prestige (triazuron) (substituting title)+TX, Trichlorphon (824)+TX, chlorobenzene second third phosphorus (trifenofos) (1455)+TX, first polynactin (trinactin) (substituting title) (653)+TX, menazon (847)+TX, fluorine pyrazoles worm (vaniliprole) [CCN] and YI-5302 (compound code)+TX,
A kind of algicide, this algicide is selected from the group be made up of following material: 3-benzo [b] thiophene-2-base-5, 6-dihydro-1, 4, 2-Evil thiazine-4-oxide compound [CCN]+TX, two cupric octoates (IUPAC title) (170)+TX, copper sulfate (172)+TX, clean (cybutryne) [CCN]+TX of spread, dihydro naphthoquinones (1052)+TX, dichlorophen (232)+TX, endothal (295)+TX, fentin (347)+TX, white lime [CCN]+TX, Parzate (566)+TX, quinoclamine (714)+TX, quinone duckweed amine (quinonamid) (1379)+TX, simazine (730)+TX, fentin acetate (IUPAC title) (347) and fentin hydroxide (IUPAC title) (347)+TX,
A kind of anthelmintic, this anthelmintic is selected from the group be made up of following material: abamectin (1)+TX, Dowco 132 (1011)+TX, doramectin (substituting title) [CCN]+TX, according to mark's fourth (291)+TX, according to mark's butylbenzene manthanoate (291)+TX, Eprinomectin (substituting title) [CCN]+TX, ivermectin (substituting title) [CCN]+TX, milbemycin (substituting title) [CCN]+TX, Moxidectin (substituting title) [CCN]+TX, piperazine [CCN]+TX, plug draws rhzomorph (substituting title) [CCN]+TX, pleocidin (737) and thiophanate (1435)+TX,
A kind of avicide, this avicide is selected from the group be made up of following material: glucochloral (127)+TX, endrin (1122)+TX, Tiguvon (346)+TX, pyridine-4-amine (IUPAC title) (23) and Strychnine (745)+TX
A kind of bactericide, this bactericide is selected from the group be made up of following material: 1-hydroxyl-1H-pyridine-2-thioketones (IUPAC title) (1222)+TX, 4-(quinoxaline-2-base is amino) benzsulfamide (IUPAC title) (748)+TX, oxine vitriol (446)+TX, bronopol (97)+TX, two cupric octoates (IUPAC title) (170)+TX, copper hydroxide (IUPAC title) (169)+TX, cresols [CCN]+TX, dichlorophen (232)+TX, Dipyrithione (1105)+TX, N-Lauryldiethylenetriaminoacetic acid (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, Versotrane (substituting title) [CCN]+TX, kasugamycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, two (dimethyl dithiocarbamate) nickel (IUPAC title) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, terramycin (611)+TX, hydroxyquinoline potassium sulfate (446)+TX, probenazole (658)+TX, Streptomycin sulphate (744)+TX, Streptomycin sulphate sesquisulfate (744)+TX, tecloftalam (766)+TX and Thiomersalate (substituting title) [CCN]+TX,
A kind of biological reagent, the group that material below this biological reagent choosing freely forms: adoxophyes moth PuGV (AdoxophyesoranaGV) (substituting title) (12)+TX, agrobacterium radiobacter (substituting title) (13)+TX, Predatory Mites (Amblyseiusspp.) (substituting title) (19)+TX, celery looper nucleopolyhedrosis virus (AnagraphafalciferaNPV) (substituting title) (28)+TX, Anagrusatomus (substituting title) (29)+TX, aphid parasitic wasp (Aphelinusabdominalis) (substituting title) (33)+TX, cotten aphid parasitic wasp (Aphidiuscolemani) (substituting title) (34)+TX, food aphid cecidomyiia (Aphidoletesaphidimyza) (substituting title) (35)+TX, autographa californica nuclear polyhedrosis virus (AutographacalifornicaNPV) (substituting title) (38)+TX, bacillus firmus (Bacillusfirmus) (substituting title) (48)+TX, Bacillus sphaericus (BacillussphaericusNeide) (formal name used at school) (49)+TX, bacillus thuringiensis (BacillusthuringiensisBerliner) (formal name used at school) (51)+TX, bacillus thuringiensis .I (Bacillusthuringiensissubsp.aizawai) (formal name used at school) (51)+TX, bacillus thuringiensis subsp israelensis (Bacillusthuringiensissubsp.israelensis) (formal name used at school) (51)+TX, bacillus thuringiensis Japan's subspecies (Bacillusthuringiensissubsp.japonensis) (formal name used at school) (51)+TX, bacillus thuringiensis k. (Bacillusthuringiensissubsp.kurstaki) (formal name used at school) (51)+TX, bacillus thuringiensis t. (Bacillusthuringiensissubsp.tenebrionis) (formal name used at school) (51)+TX, the white stiff mattress of ball spore (Beauveriabassiana) (substituting title) (53)+TX, the white stiff mattress of Bu Shi (Beauveriabrongniartii) (substituting title) (54)+TX, lacewing (Chrysoperlacarnea) (substituting title) (151)+TX, Cryptolaemus montrouzieri (Cryptolaemusmontrouzieri) (substituting title) (178)+TX,Carpocapsa pomonella granulosis virus (CydiapomonellaGV) (substituting title) (191)+TX, Dacnusa sibirica (Dacnusasibirica) (substituting title) (212)+TX, Diglyphus isaea (Diglyphusisaea) (substituting title) (254)+TX, Encarsia formosa (Encarsiaformosa) (formal name used at school) (293)+TX, eretmocerus SP (Eretmoceruseremicus) (substituting title) (300)+TX, corn earworm nucleopolyhedrosis virus (HelicoverpazeaNPV) (substituting title) (431)+TX, have a liking for mattress heterorhabditis indica (Heterorhabditisbacteriophora) and H.megidis (substituting title) (433)+TX, assemble considerable ladybug (Hippodamiaconvergens) (substituting title) (442)+TX, tangerine powder scale insect parasitic wasp (Leptomastixdactylopii) (substituting title) (488)+TX, fleahopper (Macrolophuscaliginosus) (substituting title) (491)+TX, lopper worm nucleopolyhedrosis virus (MamestrabrassicaeNPV) (substituting title) (494)+TX, Metaphycushelvolus (substituting title) (522)+TX, yellowish green green stiff mattress (Metarhiziumanisopliaevar.acridum) (formal name used at school) (523)+TX, Metarhizium anisopliae var. Anisopliae (Metarhiziumanisopliaevar.anisopliae) (formal name used at school) (523)+TX, neodiprion sertifer (Neodiprionsertifer) nucleopolyhedrosis virus and reddish tone pine bark procyanidins (N.lecontei) nucleopolyhedrosis virus (substituting title) (575)+TX, minute pirate bugs (substituting title) (596)+TX, paecilomyces fumosoroseus (Paecilomycesfumosoroseus) (substituting title) (613)+TX, Chile catches and plants mite (Phytoseiuluspersimilis) (substituting title) (644)+TX, beet armyworm (Spodopteraexiguamulticapsid) multinuclear capsid nucleopolyhedrosis virus (formal name used at school) (741)+TX, march fly nematode (Steinernemabibionis) (substituting title) (742)+TX, nematode Steinernema carpocapsae (Steinernemacarpocapsae) (substituting title) (742)+TX, Steinernema feltiae (substituting title) (742)+TX, Steinernemaglaseri (substituting title) (742)+TX,Steinernemariobrave (substituting title) (742)+TX, Steinernemariobravis (substituting title) (742)+TX, Steinernemascapterisci (substituting title) (742)+TX, genus steinernema (Steinernemaspp.) (substituting title) (742)+TX, Trichogramma spp (substituting title) (826)+TX, west blind walk mite (Typhlodromusoccidentalis) (substitute title) (844) and a lecanium wheel branch mattress (Verticilliumlecanii) (alternative title) (848)+TX,
A kind of soil disinfectant, this soil disinfectant is selected from the group be made up of following material: methyl iodide (IUPAC title) (542) and monobromomethane (537)+TX,
A kind of chemosterilant, this chemosterilant is selected from the group be made up of following material: apholate (apholate) [CCN]+TX, two (aziridine) methylamino-phosphine sulfide (bisazir) (substituting title) [CCN]+TX, busulfan (substituting title) [CCN]+TX, diflubenzuron (250)+TX, enlightening wheat is for husband (dimatif) (substituting title) [CCN]+TX, altretamine (hemel) [CCN]+TX, hempa (hempa) [CCN]+TX, metepa (metepa) [CCN]+TX, Metapside (methiotepa) [CCN]+TX, sterile spy (methylapholate) [CCN]+TX, infertile pyridine (morzid) [CCN]+TX, penfluron (penfluron) (substituting title) [CCN]+TX, Aphoxide (tepa) [CCN]+TX, sulfo-hempa (thiohempa) (substituting title) [CCN]+TX, thio-tepa (substituting title) [CCN]+TX, Tretamine (substituting title) [CCN] and uredepa (substituting title) [CCN]+TX,
A kind of insect pheromone, this insect pheromone is selected from the group be made up of following material: (E)-last of the ten Heavenly stems-5-alkene-1-yl acetate with-5-alkene-1-alcohol (IUPAC title) (222)+TX in (E)-last of the ten Heavenly stems, (E)-ten three carbon-4-alkene-1-yl acetate (IUPAC title) (829)+TX, (E)-6-methyl hept-2-ene"-4-alcohol (IUPAC title) (541)+TX, (E, Z)-ten four carbon-4,10-diene-1-yl acetate (IUPAC title) (779)+TX, (Z)-ten two carbon-7-alkene-1-yl acetate (IUPAC title) (285)+TX, (Z)-ten six carbon-11-olefine aldehydr (IUPAC title) (436)+TX, (Z)-ten six carbon-11-alkene-1-yl acetate (IUPAC title) (437)+TX, (Z)-ten six carbon-13-alkene-11-alkynes-1-yl acetate (IUPAC title) (438)+TX, (Z)-two ten-13-alkene-10-ketone (IUPAC title) (448)+TX, (Z)-ten four carbon-7-alkene-1-aldehyde (IUPAC title) (782)+TX, (Z)-ten four carbon-9-alkene-1-alcohol (IUPAC title) (783)+TX, (Z)-ten four carbon-9-alkene-1-yl acetate (IUPAC title) (784)+TX, (7E, 9Z)-ten two carbon-7,9-diene-1-yl acetate (IUPAC title) (283)+TX, (9Z, 11E)-ten four carbon-9,11-diene-1-yl acetate (IUPAC title) (780)+TX, (9Z, 12E)-ten four carbon-9,12-diene-1-yl acetate (IUPAC title) (781)+TX, 14-methyl 18-1-alkene (IUPAC title) (545)+TX, 4-methyl aldehyde C-9-5-alcohol and 4-methyl aldehyde C-9-5-ketone (IUPAC title) (544)+TX, α-many texels (multistriatin) (substituting title) [CCN]+TX, western loose bark beetle assembly pheromone (brevicomin) (substituting title) [CCN]+TX, Pherocon CM (codlelure) (substituting title) [CCN]+TX, Pherocon CM (codlemone) (substituting title) (167)+TX, cue-lure (cuelure) (substituting title) (179)+TX, Disparmone (277)+TX, 12 carbon-8-alkene-1 yl acetate (IUPAC title) (286)+TX, 12 carbon-9-alkene-1-yl acetate (IUPAC title) (287)+TX, 12 carbon-8+TX, 10-diene-1-yl acetate (IUPAC title) (284)+TX, dominicalure (substituting title) [CCN]+TX, 4-methyloctanoic acid ethyl ester (IUPAC title) (317)+TX, Eugenol (substituting title) [CCN]+TX, dendroctonus frontalis assembly pheromone (frontalin) (substituting title) [CCN]+TX, gossyplure (gossyplure) (substituting title) (420)+TX, Grandemone (grandlure) (421)+TX, Grandemone I (substituting title) (421)+TX, Grandemone II (substituting title) (421)+TX, Grandemone III (substituting title) (421)+TX, Grandemone IV (substituting title) (421)+TX, hexalure (hexalure) [CCN]+TX, ipsdienol (ipsdienol) (substituting title) [CCN]+TX, little stupid enol (ipsenol) (substituting title) [CCN]+TX, chafer gyplure (japonilure) (substituting title) (481)+TX, lineatin (substituting title) [CCN]+TX, litlure (substituting title) [CCN]+TX, looplure (looplure) (substituting title) [CCN]+TX, Medlure (medlure) [CCN]+TX, megatomoicacid (substituting title) [CCN]+TX, Allylveratrole (methyleugenol) (substituting title) (540)+TX, muscalure (muscalure) (563)+TX, ten eight-2,13-diene-1-yl acetate (IUPAC title) (588)+TX, ten eight-3,13-diene-1-yl acetate (IUPAC title) (589)+TX, He Kangbi (orfralure) (substituting title) [CCN]+TX, oryctalure (substituting title) (317)+TX, Fei Lekang (ostramone) (substituting title) [CCN]+TX, siglure (siglure) [CCN]+TX, sordidin (substituting title) (736)+TX, sulcatol (substituting title) [CCN]+TX, 14-11-alkene-1-yl acetate (IUPAC title) (785)+TX, spy lures ketone (839)+TX, spy lures ketone A (other rock) (839)+TX, spy lures ketone B
1(substituting title) (839)+TX, spy lure ketone B
2(substituting title) (839)+TX, spy lure ketone C (substituting title) (839) and trunc-call (substituting title) [CCN]+TX,
A kind of insect repellent, this insect repellent is selected from the group of following material composition: 2-(octylsulfo) ethanol (IUPAC title) (591)+TX, Indalone (butopyronoxyl) (933)+TX, butoxy (polypropylene glycol) (936)+TX, Polycizer W 260 (IUPAC title) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC title) (1048)+TX, Metadelphene [CCN]+TX, Metadelphene [CCN]+TX, Repellent 3535 (dimethylcarbate) [CCN]+TX, Rutgers 612 (1137)+TX, own urea [CCN]+TX, first quinoline fourth (methoquin-butyl) (1276)+TX, the new decyl amide of methyl [CCN]+TX, oxaminic acid ester (oxamate) [CCN] and Icaridin [CCN]+TX,
A kind of insecticide, the group of Physical Capital Stock below this insecticide choosing freely: momfluorothrin [609346-29-4]+TX, pyrazine ethiprole (pyrafluprole) [315208-17-4]+TX, flometoquin [875775-74-9]+TX, fluorine pyrrole furanone (flupyradifuron) [951659-40-8]+TX, the chloro-1-nitroethane of 1-bis-(IUPAC/ Chemical Abstracts name) (1058)+TX, 1,1-bis-chloro-2, two (4-ethylphenyl) ethane (IUPAC title) (the 1056)+TX of 2-, 1,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane and 1,3-dichloropropylene (IUPAC title) (1063)+TX, the bromo-2-chloroethanes of 1-(IUPAC/ Chemical Abstracts name) (916)+TX, acetic acid 2,2, the chloro-1-of 2-tri-(3,4-dichlorophenyl) ethyl ester (IUPAC title) (1451)+TX, phosphoric acid 2,2-dichloroethylene 2-ethylsulfinyl ethyl-methyl ester (IUPAC title) (1066)+TX, dimethyl carbamic acid 2-(1,3-dithiolane-2-yl) phenylester (IUPAC/ Chemical Abstracts name) (1109)+TX, thiocyanic acid 2-(2-Butoxyethoxy) ethyl ester (IUPAC/ Chemical Abstracts name) (935)+TX, methyl carbamic acid 2-(4,5-dimethyl-DOX-2-yl) phenylester (IUPAC/ Chemical Abstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy) ethanol (IUPAC title) (986)+TX, phosphoric acid 2-chlorovinyl diethyl ester (IUPAC title) (984)+TX, 2-imidazolone (IUPAC title) (1225)+TX, 2-isovaleryl indane-1,3-diketone (IUPAC title) (1246)+TX, methyl carbamic acid 2-methyl (Propargyl) aminophenyl ester (IUPAC title) (1284)+TX, laurate 2-Thiocyanato ethyl ester (IUPAC title) (1433)+TX, the bromo-1-chlorine of 3-third-1-alkene (IUPAC title) (917)+TX, dimethyl carbamic acid 3-methyl isophthalic acid-Phenylpyrazole-5-base ester (IUPAC title) (1283)+TX, methyl carbamic acid 4-methyl (Propargyl) amino-3,5-xylyl ester (IUPAC title) (1285)+TX, dimethyl carbamic acid 5,5-dimethyl-3-oxocyclohexyl-1-alkenyl esters (IUPAC title) (1085)+TX, abamectin (1)+TX, accephate (2)+TX, Acetamiprid (4)+TX, Acethion (substituting title) [CCN]+TX, acetyl worm nitrile [CCN]+TX,Acrinathrin (9)+TX, acrylonitrile (IUPAC title) (861)+TX, alanycarb (15)+TX, Aldicarb (16)+TX, aldoxycarb (863)+TX, drinox (864)+TX, allethrin (17)+TX, A Luo ammonia rhzomorph (substituting title) [CCN]+TX, allyxycarb (866)+TX, α-cypermethrin (202)+TX, α-moulting hormone (substituting title) [CCN]+TX, aluminum phosphate (640)+TX, match result (870)+TX, by phosphamide (872)+TX, aminocarb (873)+TX, Citram (875)+TX, oxalic acid hydrogen Citram (875)+TX, Amitraz (24)+TX, anabasine (877)+TX, ethyl methidathion (883)+TX, AVI382 (compound code)+TX, AZ60541 (compound code)+TX, nimbin (substituting title) (41)+TX, methylpyridine phosphorus (42)+TX, azinphos-methyl-ethyl (44)+TX, azinphos-methyl-methyl (45)+TX, Alamos (889)+TX, bacillus thuringiensis δ endotoxin (substituting title) (52)+TX, hexafluorosilicic acid barium (substituting title) [CCN]+TX, solbar (IUPAC/ Chemical Abstracts name) (892)+TX, smoked chrysanthemum ester [CCN]+TX, bayer 22/190 (research code) (893)+TX, Bayer 22408 (research code) (894)+TX, Ficam (58)+TX, Benfuracard micro (60)+TX, bensultap (66)+TX, β-cyfloxylate (194)+TX, β-cypermethrin (203)+TX, Biphenthrin (76)+TX, EXTHIN (78)+TX, EXTHIN S-cyclopentenyl isomers (substituting title) (79)+TX, penta ring resmethrin [CCN]+TX, biopermethrin (908)+TX, chrysron (80)+TX, two (2-chloroethyl) ether (IUPAC title) (909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenxalerate (substituting title)+TX, bromobenzene alkene phosphorus (914)+TX, bromocyclne (918)+TX, bromo-DDT (substituting title) [CCN]+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, metalkamate (924)+TX, Buprofezin (99)+TX, butacarb (926)+TX, special Pyrimitate (927)+TX, butocarboxim (103)+TX, butonate (932)+TX, butanone sulfone prestige (104)+TX, butyl pyridaben (substituting title)+TX, cadusafos (109)+TX, calcium arsenate [CCN]+TX, cyanogas (444)+TX, calcium polysulfide (IUPAC title) (111)+TX, toxaphene (941)+TX, sok (943)+TX, sevin (115)+TX,Carbofuran (118)+TX, carbon disulfide (IUPAC/ Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC title) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap (123)+TX, hydrochloric acid cartap (123)+TX, cevadine (substituting title) (725)+TX, chlorbicyclen (960)+TX, Niran (128)+TX, CD (963)+TX, Spanon (964)+TX, hydrochloric acid Spanon (964)+TX, chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenviphos (131)+TX, fluorine pyridine urea (132)+TX, chlormephos (136)+TX, chloroform [CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorine pyrazoxon (990)+TX, chlopyrifos (145)+TX, chlopyrifos-methyl (146)+TX, Actellic (994)+TX, ring worm hydrazides (150)+TX, cinerin (696)+TX, cinerin I (696)+TX, cinerin (696)+TX, cis-chrysron (substituting title)+TX, cis resmethrin (80)+TX, Cyhalothrin (substituting title)+TX, ground worm prestige (999)+TX, closantel (substituting title) [CCN]+TX, clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate [CCN]+TX, copper oleate [CCN]+TX, Resistox (174)+TX, Dithion (1006)+TX, Crotamiton (substituting title) [CCN]+TX, crotoxyphos (1010)+TX, Ruelene (1011)+TX, ice crystal (substituting title) (177)+TX, CS708 (research code) (1012)+TX, Surecide (1019)+TX, cynock (184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, second cyanogen chrysanthemum fat (188)+TX, cyfloxylate (193)+TX, Cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate (substituting title) [CCN]+TX, (R)-4-isopropenyl-1-methyl-1-cyclohexene (substituting title) [CCN]+TX, d-tetramethrin (substituting title) (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX, one first Furadan (1034)+TX, decis (223)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX,Demeton-S (1038)+TX, demeton-S-methyl (224)+TX, (demeton-S-methylsulphon) (1039)+TX is sympathized with in horizontal suction, diafenthiuron (226)+TX, dialifos (1042)+TX, diamines phosphorus (1044)+TX, basudin (227)+TX, isochlorothion (1050)+TX, dichlofenthion (1051)+TX, DDVP (236)+TX, two grams of phosphorus (substituting title)+TX, enemy carrys out dead (substituting title) [CCN]+TX, Carbicron (243)+TX, Dicyclanil (244)+TX, dieldrite (1070)+TX, 5-methylpyrazole-3-base di(2-ethylhexyl)phosphate ethyl ester (IUPAC title) (1076)+TX, diflubenzuron (250)+TX, neutraphylline (substituting title) [CCN]+TX, dimefluthrin [CCN]+TX, BFPO (1081)+TX, dimetan (1085)+TX, Rogor (262)+TX, benzyl bacterium ester (1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, Dinitrocyclohexylphenol (1089)+TX, Dinitrocyclohexylphenol (dinex-diclexine) (1089)+TX, third nitre phenol (1093)+TX, dinosam (1094)+TX, dinoseb (1095)+TX, MTI-446 (271)+TX, difenolan (1099)+TX, salithion (1100)+TX, Elacron (1101)+TX, dioxathion (1102)+TX, disulfoton (278)+TX, thiapyran phosphorus (1108)+TX, DNOC (282)+TX, doractin (substituting title) [CCN]+TX, DSP (1115)+TX, ecdysterone (substituting title) [CCN]+TX, EI1642 (research code) (1118)+TX, Affirm (Merck Co.) (291)+TX, emamectin-benzoate (291)+TX, EMPC (1120)+TX, Prallethrin (292)+TX, 5a,6,9,9a-hexahydro-6,9-methano-2,4 (294)+TX, endothion (1121)+TX, Antorane (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, protect young ether (1124)+TX, Eprinomectin (substituting title) [CCN]+TX, esfenvalerate (302)+TX, Yi Tafu kills (substituting title) [CCN]+TX, benthiocarb (308)+TX, Ethodan (309)+TX, ethiprole (310)+TX, benefit fruit-methyl (1134)+TX, phonamiphos (312)+TX, Ethyl formate (IUPAC title) [CCN]+TX, ethyl-DDD (substituting title) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride (chemical name) (1136)+TX, oxirane [CCN]+TX,Ether chrysanthemum ester (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, Dovip (323)+TX, Nemacur (326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, ethylbenzene prestige (1149)+TX, fenfluthrin (1150)+TX, fenifrothion (335)+TX, Bassa (336)+TX, non-Nochlin (1153)+TX, fenoxycarb (340)+TX, fenpirithrin (1155)+TX, Fenpropathrin (342)+TX, tebufenpyrad (substituting title)+TX, fensulfothion (1158)+TX, Entex (346)+TX, Entex-ethyl [CCN]+TX, fenvalerate (349)+TX, ethiprole (354)+TX, fluorine Buddhist nun amine (358)+TX, fipronil bisamide (CAS number of registration: 272451-65-7)+TX, volt health urea (1168)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, Fluenyl (1169)+TX, phonetic worm amine [CCN]+TX, Flufenoxuron (370)+TX, trifluoro (1171)+TX, flumethrin (372)+TX, taufluvalinate (1184)+TX, FMC1137 (research code) (1185)+TX, Dyfonate (1191)+TX, medimeform (405)+TX, hydrochloric acid medimeform (405)+TX, peace fruit (1192)+TX, amine first prestige (1193)+TX, fosmethilan (1194)+TX, fospirate (1195)+TX, lythidathion (408)+TX, fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX, γ-Cyhalothrin (197)+TX, γ-HCH (430)+TX, Guanoctine (422)+TX, acetic acid Guanoctine (422)+TX, GY-81 (research code) (423)+TX, halfenprox (424)+TX, chlorine worm hydrazides (425)+TX, HCH (430)+TX, HEOD (1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, speed is killed sulphur phosphorus [CCN]+TX, HEXAFLUMURON (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX, hydrogen cyanide (444)+TX, hydroprene (445)+TX, put forth energy to drench prestige (1223)+TX, Imidacloprid (458)+TX, Imiprothrin (460)+TX, indoxacarb (465)+TX, iodomethane (IUPAC title) (542)+TX, IPSP (1229)+TX, fenamiphos (1231)+TX, Telodrin (1232)+TX, isocarbophos (substituting title) (473)+TX, isodrin (1235)+TX, isofenphos (1236)+TX, transplant spirit (1237)+TX,Isoprocarb (472)+TX, O-(Methoxyamino thiophosphoryl) salicylic acid isopropyl esters (IUPAC title) (473)+TX, Isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX, ivermectin (substituting title) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, iodfenphos (1248)+TX, juvenile hormone I (substituting title) [CCN]+TX, juvenile hormone II (substituting title) [CCN]+TX, juvenile hormone III (substituting title) [CCN]+TX, chlorine penta encircles (1249)+TX, kinoprene (484)+TX, λ-Cyhalothrin (198)+TX, lead arsenate [CCN]+TX, thunder cuticulin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, pyridine worm phosphorus (1251)+TX, Lufenuron (490)+TX, lythidathion (1253)+TX, cumenyl ester between methyl carbamic acid (IUPAC title) (1014)+TX, magnesium phosphide (IUPAC title) (640)+TX, malathion (492)+TX, third mite cyanogen (1254)+TX, mazidox (1255)+TX, Afos (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan (1261)+TX, calogreen (513)+TX, first oxydemeton_methyl (1263)+TX, metaflumizone (CCN)+TX, metham-sodium (519)+TX, metham-sodium-potassium (substituting title) (519)+TX, metham-sodium-sodium (519)+TX, methacrifos (1266)+TX, acephatemet (527)+TX, fluoridize mesyl (IUPAC/ Chemical Abstracts name) (1268)+TX, methidathion (529)+TX, mercaptodimethur (530)+TX, desinsection ethephon (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, quinacrine-butyl (1276)+TX, methothrin (substituting title) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methyl bromide (537)+TX, methyl-isorhodanate (543)+TX, methyl chloroform (substituting title) [CCN]+TX, chloromethane [CCN]+TX, metofluthrin [CCN]+TX, MTMC (550)+TX, metoxadiazone (1288)+TX, Menite (556)+TX, mexacarbate (1290)+TX, the close spit of fland of going out (557)+TX, milbemycin oxime (substituting title) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, Azodrin (561)+TX, morphothion (1300)+TX, Moxidectin (substituting title) [CCN]+TX, Naftalofos (substituting title) [CCN]+TX,2-dichloroethylk dimethyl phosphate (567)+TX, naphthalene (IUPAC/ Chemical Abstracts name) (1303)+TX, NC-170 (research code) (1306)+TX, NC-184 (compound code)+TX, nicotine (578)+TX, nicotine sulphate (578)+TX, nifluridide (1309)+TX, Nitenpyram (579)+TX, nithiazide (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex compound (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, nornicotine (traditional title) (1319)+TX, Rimon (585)+TX, noviflumuron (586)+TX, the chloro-4-iodophenyl O-of ethylenebis dithiocarbamate phosphonic acids O-5-bis-ethyl ester (IUPAC title) (1057)+TX, D2EHDTPA O, O-diethyl O-4-methyl-2-oxo-2H-chromene-7-base ester (IUPAC title) (1074)+TX, D2EHDTPA O, O-diethyl O-6-methyl-2-propyl pyrimidine-4-yl ester (IUPAC title) (1075)+TX, two sulfo-pyrophosphoric acid O, O, O ', O '-tetrapropyl ester (IUPAC title) (1424)+TX, oleic acid (IUPAC title) (593)+TX, omethoate (594)+TX, oxamoyl (602)+TX, oxydemeton_methyl (oxydemeton-methyl) (609)+TX, oxydeprofos (1324)+TX, Disystom-s (1325)+TX, pp ' O '-tetrapropyl two thiopyrophosphate (IUPAC title) (1424)+TX, octadecenic acid (IUPAC title) (593)+TX, omethoate (omethoate) (594)+TX, oxamoyl (602)+TX, metilomerkaptofosoksid (oxydemeton-methyl) (609)+TX, oxydeprofos (1324)+TX, Disystom-s (1325)+TX, pp '-DDT (219)+TX, paracide [CCN]+TX, parathion (615)+TX, parathion-methyl (616)+TX, penfluron (substituting title) [CCN]+TX, pentachlorophenol (623)+TX, laurate five chlorophenyl ester (IUPAC title) (623)+TX, permethrin (626)+TX, oil (substituting title) (628)+TX, PH60-38 (research code) (1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate dimephenthoate cidial (631)+TX, thimet (636)+TX, zolone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, nichlorfos (1339)+TX, phosphamidon (639)+TX, phosphine (IUPAC title) (640)+TX, phoxim (642)+TX,Phoxim-methyl (1340)+TX, methylamine phosphorus (the 1344)+TX that crows, Aphox (651)+TX, Diothyl-ethyl (1345)+TX, Diothyl-methyl (652)+TX, polychlorostyrene bicyclopentadiene isomers (IUPAC title) (1346)+TX, polychlorostyrene terpenes (traditional title) (1347)+TX, potassium arsenite [CCN]+TX, potassium rhodanide [CCN]+TX, prallethrin (655)+TX, precocene I (substituting title) [CCN]+TX, precocene II (substituting title) [CCN]+TX, precocene III (substituting title) [CCN]+TX, acetyl pyrimidine phosphorus (1349)+TX, Profenofos (662)+TX, the third Flumethrin [CCN]+TX, promacyl (1354)+TX, Carbamult (1355)+TX, Kayaphos (1356)+TX, Propetamphos (673)+TX, arprocarb (678)+TX, prothidathion (1360)+TX, Toyodan (686)+TX, prothoate (1362)+TX, propyl benzene hydrocarbon chrysanthemum ester [CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, Ppyrazophos (693)+TX, anti-Chryson (1367)+TX, pyrethrins I (696)+TX, chrysanthemumdicarboxylic acid monomethyl ester pyrethrolone ester (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphethione (701)+TX, pyrimidifen (706)+TX, Pyrimitate (1370)+TX, Nylar (708)+TX, quassia (substituting title) [CCN]+TX, diethquinalphione (711)+TX, diethquinalphione-methyl (1376)+TX, raise peaceful phosphorus (1380)+TX, quinalphos (1381)+TX, R-1492 (research code) (1382)+TX, iodo-ether salicylamine (substituting title) [CCN]+TX, chrysron (719)+TX, rotenone (722)+TX, RU15525 (research code) (723)+TX, RU25475 (research code) (1386)+TX, ryania (substituting title) (1387)+TX, ryanodine (traditional title) (1387)+TX, sabadilla (substituting title) (725)+TX, schradane (1389)+TX, gram line pellet (substituting title)+TX, selamectin (substituting title) [CCN]+TX, SI-0009 (compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compound code)+TX, silafluofene (728)+TX, SN72129 (research code) (1397)+TX, sodium arsenite [CCN]+TX, Cymag (444)+TX, sodium fluoride (IUPAC/ Chemical Abstracts name) (1399)+TX,Sodium hexafluorisilicate (1400)+TX, penta sodium pentachlorophenate (623)+TX, sodium selenate (IUPAC title) (1401)+TX, sodium sulfocyanate [CCN]+TX, sophamide (1402)+TX, pleocidin (737)+TX, Spiromesifen (739)+TX, spiral shell worm ethyl ester [CCN]+TX, grand (the 746)+TX of sulphur phenylate, sulphur phenylate is grand-sodium (746)+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfur fluoride acyl group (756)+TX, sulprofos (1408)+TX, tar (substituting title) (758)+TX, taufluvalinate (tau-fluvalinate) (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX, worm hydrazides (762)+TX, tebufenpyrad (763)+TX, butyl pyrimidine phosphorus (764)+TX, fluorobenzene urea (768)+TX, Tefluthrin (769)+TX, Swebate (770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam (substituting title)+TX, Terbufos (773)+TX, tetrachloroethanes [CCN]+TX, Ravap (777)+TX, tetramethrin (787)+TX, θ-cypermethrin (204)+TX, thiacloprid (791)+TX, the fragrant promise of thiophene (substituting title)+TX, Diacloden (792)+TX, benzene thiophene sulphur phosphorus (1428)+TX, Talcord (1431)+TX, thiocyclam (798)+TX, oxalic acid hydrogen thiocyclam (798)+TX, sulphur enemy gram (799)+TX, thiofanox (800)+TX, thiometon (801)+TX, nemaphos (1434)+TX, dimehypo (803)+TX, dimehypo (thiosultap-sodium) (803)+TX, thuringiensin (substituting title) [CCN]+TX, Tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX, anti-Permethrin (1440)+TX, triamiphos (1441)+TX, triaguron (818)+TX, Hostathion (820)+TX, azoles prestige (substituting title)+TX, trichlorfon 98 (824)+TX, different Nankor-3 (substituting title) [CCN]+TX, trichloronat (1452)+TX, trichlorine third oxygen phosphorus (1455)+TX, grand (the 835)+TX of desinsection, Landrin (840)+TX, triprene (1459)+TX, Kilval (847)+TX, fluorine pyrazoles worm [CCN]+TX, veratridine (substituting title) (725)+TX, jervine (substituting title) (725)+TX, XMC (853)+TX, Meobal (854)+TX, YI-5302 (compound code)+TX, ξ-cypermethrin (205)+TX, own body cypermethrin (substituting title)+TX,Zinc phosphide (640)+TX, the general phosphorus of Zola (1469) and ZXI8901 (research code) (858)+TX, bromine cyanogen insect amide [736994-63-19]+TX, Rynaxypyr [500008-45-7]+TX, azoles mite cyanogen [560121-52-0]+TX, cyflumetofen [400882-07-7]+TX, fluorine worm pyrrole quinoline [337458-27-2]+TX, ethyl pleocidin [187166-40-1+187166-15-0]+TX, spiral shell worm ethyl ester [203313-25-1]+TX, fluorine pyridine worm amine nitrile [946578-00-3]+TX, butene-fipronil [704886-18-0]+TX, chlorine fluorine ether chrysanthemum ester [915288-13-0]+TX, etrafluorine ethofenprox [84937-88-2]+TX and a kind of there is chemical formula B1 compound
(there is common name triflumezopyrim (being disclosed in WO2012/092115))+TX;
A kind of invertebrate poison, this invertebrate poison is selected from the group be made up of following material: two (tributyl tin) oxide compound (IUPAC title) (913)+TX, bromoacetamide [CCN]+TX, Tricalcium arsenate [CCN]+TX, cloethocarb (cloethocarb) (999)+TX, Vienna green [CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, tertiary iron phosphate (IUPAC title) (352)+TX, the methaldehyde (518)+TX, metmercapturon (530)+TX, niclosamide (576)+TX, Clonitrilide (576)+TX, Pentachlorophenol (623)+TX, pentachlorobenzene sodium oxide (623)+TX, tazimcarb (tazimcarb) (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (trifenmorph) (1454)+TX, trimethacarb (trimethacarb) (840)+TX, triphenyltin acetate (IUPAC title) (347) and fentin hydroxide (IUPAC title) (347)+TX, Pi Ruipu (pyriprole) [394730-71-3]+TX,
A kind of nematocides, this nematocides is selected from the group be made up of following material: AKD-3088 (compound code)+TX, the bromo-3-chloropropane of 1,2-bis-(IUPAC/ chemical abstracts name) (1045)+TX, 1,2-propylene dichloride (IUPAC/ chemical abstracts name) (1062)+TX, 1,2-propylene dichloride and 1,3-dichloropropylene (IUPAC title) (1063)+TX, 1,3-dichloropropylene (233)+TX, 3,4-dichloro tetramethylene sulfide 1,1-dioxide (IUPAC/ chemical abstracts name) (1065)+TX, 3-(4-chloro-phenyl-)-5-methyl rhodanine (IUPAC title) (980)+TX, 5-methyl-6-sulfo--1,3,5-thiadiazine alkane-3-guanidine-acetic acid (IUPAC title) (1286)+TX, 6-isopentene group aminopurine (substituting title) (210)+TX, abamectin (1)+TX, acetyl worm nitrile [CCN]+TX, alanycarb (15)+TX, aldicarb (aldicarb) (16)+TX, aldoxycarb (aldoxycarb) (863)+TX, AZ60541 (compound code)+TX, benclothiaz [CCN]+TX, benzene mattress spirit (62)+TX, butyl pyridaben (butylpyridaben) (substituting title)+TX, cadusafos (cadusafos) (109)+TX, carbofuran (carbofuran) (118)+TX, dithiocarbonic anhydride (945)+TX, carbosulfan (119)+TX, trichloronitromethane (141)+TX, Chlorpyrifos 94 (145)+TX, cloethocarb (cloethocarb) (999)+TX, phytokinin (cytokinins) (substituting title) (210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, Nellite (diamidafos) (1044)+TX, dichlofenthion (dichlofenthion) (1051)+TX, two grams of phosphorus (dicliphos) (substituting title)+TX, Rogor (262)+TX, according to mark's fourth (substituting title) [CCN]+TX, phenylformic acid is according to mark's fourth (291)+TX, Eprinomectin (291)+TX, (substituting title) [CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (fenamiphos) (326)+TX, tebufenpyrad (substituting title)+TX, fensulfothion (fenpyrad) (1158)+TX, lythidathion (fosthiazate) (408)+TX, fosthietan (fosthietan) (1196)+TX, furfural (substituting title) [CCN]+TX, GY-81 (research code) (423)+TX, speed kills sulphur phosphorus (heterophos) [CCN]+TX, methyl iodide (IUPAC title) (542)+TX, isamidofos (1230)+TX, isazofos (isazofos) (1231)+TX, kinetin (kinetin) (substituting title) [CCN]+TX, chaff aminopurine (mecarphon) (substituting title) (210)+TX, mecarphon (mecarphon) (1258)+TX, metamsodium (519)+TX, metamsodium sylvite (substituting title) (519)+TX, metamsodium sodium salt (519)+TX, monobromomethane (537)+TX, Trapex (543)+TX, polynactin oxime (milbemycinoxime) (substituting title) [CCN]+TX, Moxidectin (picking name) [CCN]+TX, wart spore paint spot mattress (Myrotheciumverrucaria) component (substituting title) (565)+TX, NC-184 (compound code)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosphorus worm prestige (phosphocarb) [CCN]+TX, cadusafos (sebufos) (substituting title)+TX, plug draws rhzomorph (selamectin) (substituting title) [CCN]+TX, pleocidin (737)+TX, terbam (terbam) (substituting title)+TX, Terbufos (terbufos) (773)+TX, tetrachlorothiophene (IUPAC/ chemical abstracts name) (1422)+TX, thiafenox (substituting title)+TX, thionazin (thionazin) (1434)+TX, triazophos (triazophos) (820)+TX, triazuron (substituting title)+TX, xylenol [CCN]+TX, YI-5302 (compound code) and zeatin (substituting title) (210)+TX, fluensulfone [318290-98-1]+TX,
A kind of nitrification inhibitor, this nitrification inhibitor is selected from the group be made up of following material: potassium ethyl xanthonate [CCN] and chlorine pyridine (nitrapyrin) (580)+TX,
A kind of activating plants agent, this activating plants agent is selected from the group be made up of following material: thiadiazoles element (acibenzolar) (6)+TX, thiadiazoles element-S-methyl (6)+TX, probenazole (probenazole) (658) and large giant knotweed (Reynoutriasachalinensis) extract (substituting title) (720)+TX
A kind of rodenticide, this rodenticide is selected from the group be made up of following material: 2-isovaleryl indane-1,3-diketone (IUPAC title) (1246)+TX, 4-(quinoxaline-2-base is amino) benzsulfamide (IUPAC title) (748)+TX, alpha-chloro alcohol [CCN]+TX, aluminium phosphide (640)+TX, safe and reliable (880)+TX, white arsenic (882)+TX, barium carbonate (891)+TX, two mouse urea (912)+TX, Talon (89)+TX, bromadiolone (91)+TX, bromethalin (92)+TX, calcyanide (444)+TX, Chloralose (127)+TX, chlorophacinone (140)+TX, Vitamin D3 500,000 I.U/GM (substituting title) (850)+TX, coumachlor (1004)+TX, Fumarin (1005)+TX, kill mouse naphthalene (175)+TX, crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, sodium diphacinone (273)+TX, vitamin D2 (301)+TX, flocoumafen (357)+TX, monofluoroacetamide (379)+TX, mouse Piao Ding (1183)+TX, hydrochloric acid mouse Piao Ding (1183)+TX, γ-HCH (430)+TX, HCH (430)+TX, prussic acid (444)+TX, methyl iodide (IUPAC title) (542)+TX, woods dawn (430)+TX, magnesium phosphide (IUPAC title) (640)+TX, monobromomethane (537)+TX, norbormide (1318)+TX, Gophacide (1336)+TX, phosphuret-(t)ed hydrogen (IUPAC title) (640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, Sodium metaarsenite [CCN]+TX, sodium cyanide (444)+TX, Tenate (fluoroacetate) (735)+TX, Strychnine (745)+TX, thallic sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,
A kind of synergistic agent, this synergistic agent is selected from the group be made up of following material: 2-(2-Butoxyethoxy) ethyl piperonyl ester (IUPAC title) (934)+TX, 5-(1, 3-benzodioxole-5-base)-3-hexyl hexamethylene-2-ketenes (IUPAC title) (903)+TX, there is farnesol (substituting title) (324)+TX of nerolidol, MB-599 (research code) (498)+TX, MGK264 (research code) (296)+TX, Piperonyl Butoxide (piperonylbutoxide) (649)+TX, Piprotal (piprotal) (1343)+TX, propylisome (propylisomer) (1358)+TX, S421 (research code) (724)+TX, Safroxan (sesamex) (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,
A kind of animal repellent, this animal repellent is selected from the group be made up of following material: anthraquinone (32)+TX, glucochloral (127)+TX, copper naphthenate [CCN]+TX, Cupravit (171)+TX, diazinon (227)+TX, Dicyclopentadiene (DCPD) (chemical name) (1069)+TX, Guanoctine (422)+TX, biguanides acetate (422)+TX, metmercapturon (530)+TX, pyridine-4-amine (IUPAC title) (23)+TX, plug logical sequence (804)+TX, trimethacarb (trimethacarb) (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX,
A kind of virucide, this virucide is selected from the group be made up of following material: imanin (imanin) (substituting title) [CCN] and ribavirin (substituting title) [CCN]+TX,
A kind of wound protective material, this wound protective material is selected from the group be made up of following material: red precipitate (512)+TX, octhilinone (octhilinone) (590) and methyl sulphur mattress spirit (802)+TX,
And bioactive compound, this compound is selected from the group of following material composition: Rodewod (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole [119446-68-3]+TX, olefin conversion [83657-24-3]+TX, epoxiconazole [106325-08-0]+TX, RH-7592 [114369-43-6]+TX, fluquinconazole [136426-54-5]+TX, fluzilazol [85509-19-9]+TX, flutriafol [76674-21-0]+TX, own azoles alcohol [79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole [86598-92-7]+TX, plant bacterium azoles [125225-28-7]+TX, metconazole [125116-23-6]+TX, nitrile bacterium azoles [88671-89-0]+TX, pefurazoate [101903-30-4]+TX, Topaze [66246-88-6]+TX, prothioconazoles [178928-70-6]+TX, pyrifenox (pyrifenox) [88283-41-4]+TX, Prochloraz [67747-09-5]+TX, Wocosin 50TK [60207-90-1]+TX, simeconazoles (simeconazole) [149508-90-7]+TX, tebuconazole [107534-96-3]+TX, fluorine ether azoles [112281-77-3]+TX, triazolone [43121-43-3]+TX, triazolone [55219-65-3]+TX, fluorine bacterium azoles [99387-89-0]+TX, triticonazole [131983-72-7]+TX, three ring benzene phonetic alcohol [12771-68-5]+TX, fenarimol [60168-88-9]+TX, fluorochlorobenzene ancymidol [63284-71-9]+TX, bupirimate (bupirimate) [41483-43-6]+TX, Milcurb (dimethirimol) [5221-53-4]+TX, Milstem (ethirimol) [23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidin (fenpropidine) [67306-00-7]+TX, fenpropimorph [67564-91-4]+TX, volution bacterium amine [118134-30-8]+TX, tridemorph [81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim [110235-47-7]+TX, phonetic mould amine (pyrimethanil) [53112-28-0]+TX, fenpiclonil [74738-17-3]+TX, fludioxonil (fludioxonil) [131341-86-1]+TX, M 9834 (benalaxyl) [71626-11-4]+TX, furalaxyl (furalaxyl) [57646-30-7]+TX, metaxanin [57837-19-1]+TX, R-metaxanin [70630-17-0]+TX, ofurace [58810-48-3]+TX, Wakil (Oxadixyl) [77732-09-3]+TX, F-1991 [17804-35-2]+TX, derosal [10605-21-7]+TX, debacarb (debacarb) [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, Thiabendazole [148-79-8]+TX, chlozolinate (chlozolinate) [84332-86-5]+TX, dichlozolin (dichlozoline) [24201-58-9]+TX, RP-26019 (Iprodione) [36734-19-7]+TX, myclozoline [54864-61-8]+TX, procymidone (procymidone) [32809-16-8]+TX, Vinclozoline (vinclozoline) [50471-44-8]+TX, boscalid amine (boscalid) [188425-85-6]+TX, carboxin [5234-68-4]+TX, first furan anilide [24691-80-3]+TX, fultolanil (Flutolanil) [66332-96-5]+TX, mebenil [55814-41-0]+TX, oxycarboxin [5259-88-1]+TX, pyrrole metsulfovax (penthiopyrad) [183675-82-3]+TX, thiophene methuroxam [130000-40-7]+TX, Guanoctine [108173-90-6]+TX, dodine (dodine) [2439-10-3] [112-65-2] (free key)+TX, iminoctadine (iminoctadine) [13516-27-3]+TX, Azoxystrobin [131860-33-8]+TX, mandestrobin [173662-97-0]+TX, dimoxystrobin [149961-52-4]+TX, enostroburin { Proc.BCPC, Int.Congr., Glasgow.2003,1,93}+TX, fluoxastrobin [361377-29-9]+TX, methyl kresoxim-methyl [143390-89-0]+TX, SSF 126 [133408-50-1]+TX, oxime bacterium ester [141517-21-7]+TX, orysastrobin [248593-16-0]+TX, ZEN 90160 [117428-22-5]+TX, Strobilurin [175013-18-0]+TX, Karbam Black [14484-64-1]+TX, 3-[5-(4-chloro-phenyl-)-2,3-dimethyl-3-isoxazole alkyl] pyridine (SYP-Z048), zinc manganese ethylenebisdithiocarbamate [8018-01-7]+TX, maneb [12427-38-2]+TX, Carbatene [9006-42-2]+TX, antracole (propineb) [12071-83-9]+TX, plug logical sequence [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX, Difolatan (captafol) [2425-06-1]+TX, Vancide 89 [133-06-2]+TX, dichlofluanid [1085-98-9]+TX, ethofumesate (fluoroimide) [41205-21-4]+TX, Phaltan [133-07-3]+TX, Tolylfluanid [731-27-1]+TX, Bordeaux (bordeaux) mixture [8011-63-0]+TX, copper hydroxide (copperhydroxid) [20427-59-2]+TX, cupric chloride (copperoxychlorid) [1332-40-7]+TX, copper sulfate (coppersulfat) [7758-98-7]+TX, cupric oxide (copperoxid) [1317-39-1]+TX, mancopper (mancopper) [53988-93-5]+TX, oxinecopper (oxine-copper) [10380-28-6]+TX, dinocap (dinocap) [131-72-6]+TX, nitrothalisopropyl (nitrothal-isopropyl) [10552-74-6]+TX, Hinosan [17109-49-8]+TX, iprobenfos (iprobenphos) [26087-47-8]+TX, isoprothiolane (isoprothiolane) [50512-35-1]+TX, phosdiphen (phosdiphen) [36519-00-3]+TX, gram bacterium phosphorus (pyrazophos) [13457-18-6]+TX, methyl holder chlorine phosphorus (tolclofos-methyl) [57018-04-9]+TX, diazosulfide (acibenzolar-S-methyl) [135158-54-2]+TX, anilazine [101-05-3]+TX, benzene metsulfovax [413615-35-7]+TX, miewensu (blasticidin)-S [2079-00-7]+TX, chinomethionate (chinomethionat) [2439-01-2]+TX, chloroneb (chloroneb) [2675-77-6]+TX, m-tetrachlorophthalodinitrile [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, frost urea cyanogen [57966-95-7]+TX, dichlone (dichlone) [117-80-6]+TX, two chlorine zarilamid (diclocymet) [139920-32-4]+TX, diclomezin (diclomezine) [62865-36-5]+TX, dicloran (dicloran) [99-30-9]+TX, the mould prestige of second (diethofencarb) [87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph) [211867-47-9]+TX, Delan (dithianon) [3347-22-6]+TX, Guardian (ethaboxam) [162650-77-3]+TX, etridiazole (etridiazole) [2593-15-9]+TX, Famoxate [131807-57-3]+TX, fenamidone (fenamidone) [161326-34-7]+TX, fenoxanil (Fenoxanil) [115852-48-7]+TX, fentin (fentin) [668-34-8]+TX, ferimzone (ferimzone) [89269-64-7]+TX, fluazinam (fluazinam) [79622-59-6]+TX, fluopicolide (fluopicolide) [239110-15-7]+TX, flusulfamide (flusulfamide) [106917-52-6]+TX, fenhexamid [126833-17-8]+TX, Fu Sai get (fosetyl-aluminium) [39148-24-8]+TX, dislike mould spirit (hymexazol) [10004-44-1]+TX, zinc 1,2-propylene bisdithiocarbamate [140923-17-7]+TX, IKF-916 (match seat goes out (Cyazofamid)) [120116-88-3]+TX, kasugamycin (kasugamycin) [6980-18-3]+TX, methasulfocarb (methasulfocarb) [66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron (pencycuron) [66063-05-6]+TX, phthalide [27355-22-2]+TX, Polyoxin (polyoxins) [11113-80-7]+TX, thiabendazole (probenazole) [27605-76-1]+TX, hundred dimension prestige (propamocarb) [25606-41-1]+TX, iodine quinazolone (proquinazid) [189278-12-4]+TX, happy quinoline ketone (pyroquilon) [57369-32-1]+TX, quinoxyfen [124495-18-7]+TX, Tritisan [82-68-8]+TX, sulphur [7704-34-9]+TX, tiadinil [223580-51-6]+TX, triazoxide (triazoxide) [72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (zoxamide) (RH7281) [156052-68-5]+TX, mandipropamid (mandipropamid) [374726-62-2]+TX,
And SDHI inhibitor, this SDHI inhibitor is selected from by the following group formed
Fluorine azoles bacterium aniline ([494793-67-8], US7538073 (N-[2-(1, 3-dimethylbutyl) phenyl]-5-fluoro-1, 3-dimethyl-1H-pyrazole-4-carboxamide)+TX, good fortune Lapie ([123572-88-3] (chloro-N-(1 of 5-, 3-dihydro-1, 1, 3-trimethylammonium-4-isobenzofuran-base)-1, 3-dimethyl-1H-pyrazole-4-carboxamide)+TX, pyrrole metsulfovax (US5747518, [183675-82-3], (N-[2-(1, 3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide)+TX, biphenyl pyrrole bacterium amine (US7329633, [581809-46-3], (N-(3 ', 4 '-two chloro-5-fluorine [1, 1 '-phenylbenzene]-2-base)-3-(difluoromethyl)-1-methyl isophthalic acid H-pyrazole-4-carboxamide)+TX, different piperazine draws praises (US7598395, [881685-58-1] (2yn-isomers 3-(difluoromethyl)-1-methyl-N-[(1RS, 4SR, 9RS)-1, 2, 3, 4-tetrahydrochysene-9-sec.-propyl-1, 4-methyl alcohol naphthalene-5-base] pyrazole-4-carboxamide and 2anti-isomers 3-(difluoromethyl)-1-methyl-N-[(1RS, 4SR, 9SR)-1, 2, 3, 4-tetrahydrochysene-9-sec.-propyl-1, 4-methyl alcohol naphthalene-5-base] mixture of pyrazole-4-carboxamide)+TX, fluorine azoles ring bacterium amine (EP1480955B1, [874967-67-6] (2 cis-isomers, 2 '-[(1RS, 2RS)-1, 1 '-two ring third-2-base]-3-(difluoromethyl)-1-methylpyrazole-4-anilino formyl and 2 trans-isomers 2 '-[(1RS, 2SR)-1, 1 '-two ring third-2-base] mixture of-3-(difluoromethyl)-1-methylpyrazole-4-anilino formyl)+TX, fluorine azoles bacterium acid amides (US8008232, [907204-31-3] (3-(difluoromethyl)-1-methyl-N-(3 ', 4 ', 5 '-trifluoro [1, 1 '-phenylbenzene]-2-base)-1H-pyrazole-4-carboxamide)+TX, solatenol (WO2007/048556 (3-difluoromethyl-1-methyl isophthalic acid H-pyrazoles-4-carboxylic acid (9-dichloro methylene-1, 2, 3, 4-tetrahydrochysene-1, 4-methyl alcohol-naphthalene-5-base)-acid amides)+TX, compound 3-(difluoromethyl)-N-methoxyl group-1-methyl-N-[1-methyl-2-(2, 4, 6-trichlorophenyl) ethyl] pyrazole-4-carboxamide (describing in WO2010/063700)+TX, thiophene fluorine bacterium amine (thifluzamide) (US5045554, [130000-40-7] (N-[2, the bromo-4-of 6-bis-(trifluoromethoxy) phenyl]-2-methyl-4-(trifluoromethyl)-5-thiazole carboxamides)+TX, boscalid amine (US5589493, [188425-85-6 (the chloro-N-of 2-(4 '-chlorine [1, 1 '-phenylbenzene]-2-base)-Niacinamide)+TX, oxycarboxin ([5259-88-1] (5, 6-dihydro-2-Methyl-N-phenyl-1, 4-oxathiin-3-methane amide 4, 4-dioxide, )+TX, carboxin ([5234-68-4] (5, 6-dihydro-2-Methyl-N-phenyl-1, 4-oxathiin-3-methane amide)+TX, fluorine pyrrole bacterium acid amides (US7572818, [658066-35-4]), (N-[2-[the chloro-5-of 3-(trifluoromethyl)-2-pyridyl] ethyl]-2-(trifluoromethyl) benzamide)+TX, fluorine Mepronil ([24691-80-3], (2-Methyl-N-phenyl-3-furoylamide, phenol bacterium fluorine comes), US4093743, number of registration 66332-96-5 (N-[3-(1-methyl ethoxy) phenyl]-2-(trifluoromethyl) benzamide)+TX, mebenil ([55814-41-0], (2-methyl-N-[3-(1-methyl ethoxy) phenyl] benzamide)+TX and benodanil ([15310-01-7], (the iodo-N-phenylbenzamaide of 2-)+TX,
And compound [(3S, 4R, 4aR, 6S, 6aS, 12R, 12aS, 12bS)-3-[(cyclopropyl carbonyl) oxygen base]-1, 3, 4, 4a, 5, 6, 6a, 12, 12a, 12b-decahydro-6, 12-dihydroxyl-4, 6a, 12b-trimethylammonium-11-oxygen-9-(3-pyridyl)-2H, 11H naphtho-[2, 1-b] pyrans also [3, 4-e] pyrans-4-base] methyl-cyclopropane manthanoate [915972-17-7]+TX, 1, 3, 5-trimethylammonium-N-(2-methyl isophthalic acid-oxygen propyl group)-N-[3-(2-methyl-propyl)-4-[2, 2, the fluoro-1-methoxyl group of 2-tri--1-(trifluoromethyl) ethyl] phenyl]-1H-pyrazole-4-carboxamide [926914-55-8]+TX and 4-oxygen-4-[(2-phenylethyl) is amino]-butyric acid (being disclosed in WO2010/137677)+TX.
The registration number referring to chemical abstracts see, for example [3878-19-1] in bracket after activeconstituents.Hybrid combination thing described above is known.When activeconstituents is included in " pesticides handbook (ThePesticideManual) " [pesticides handbook-global overview (ThePesticideManual-AWorldCompendium); 13rd edition; Write: C.D.S. Tom woods (TomLin); British Crop protective committee (ThePesticideManual-AWorldCompendium; ThirteenthEdition; Editor:C.D.S.TomLin; TheBritishCropProtectionCouncil) time], they above for being described in this handbook under the entry number given in parenthesis of specific compound; Such as, compound " abamectin " describes under entry number (1).When above " [CCN] " is added to concrete compound time, during the compound discussed is included in " agricultural chemicals popular name outline (CompendiumofPesticideCommonNames) ", this outline can obtain on the internet: [A.Wood (Wood);
agricultural chemicals popular name outline, copyright
1995-2013]; Such as compound " acetyl worm nitrile " is in the Internet address
http:// www.alanwood.net/pesticides/ acetoprole.htmlunder be described.
In above-mentioned activeconstituents, major part is mentioned by so-called " popular name ", relevant " ISO popular name " or another " popular name " of using on rare occasion above.If title is not " popular name ", so specific compound is given instead in parenthesis and the character of this title used; In this case, use IUPAC title, IUPAC/ Chemical Abstracts name, " chemical name ", " traditional title ", " compound title " or " research code ", if or both do not use one of these titles, also do not use " popular name ", so use " substituting title ".
Be selected from table 1 and comprise a kind of compound and the above-mentioned activeconstituents of one that are selected from table 1 to 130 to 168 and the compound with Formula I of V1 to V26 and the mixture of active principles of above-mentioned activeconstituents, preferably be in the mixture ratio from 100:1 to 1:6000, especially from 50:1 to 1:50, more particularly be in the ratio from 20:1 to 1:20, even more specifically from 10:1 to 1:10, very especially, from 5:1 and 1:5, especially preferred is that ratio from 2:1 to 1:2 provides, and the ratio from 4:1 to 2:1 is preferred equally, particularly be in 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or the ratio of 4:750.The ratio that these mixture ratios are by weight.
Mixture described above can be used to control in the method for harmful organism, the method comprises and is applied in harmful organism or its environment by a kind of composition containing mixture as described above, except a kind of by operation or therapy for the treatment of the method for human or animal body and the diagnostic method implemented for human or animal body.
Comprise and be selected from table 1 and can such as use with the form of a kind of single " ready-mix " to 168 and the compound with Formula I of V1 to V26 and the mixture of one or more activeconstituentss as described above, use with the spraying mixture (this mixture is made up of the independent preparation of these single-activity compositions) of combination (such as a kind of " bucket mix formulation "), and work as in a kind of mode of order (namely, one after another appropriateness short period, such as several hours or several days) combinationally use these independent activeconstituentss when using and use.Use and be selected from table 1 to 168 and these of V1 to V26 and there is the compound of Formula I and the order of above-mentioned activeconstituents is not vital for enforcement the present invention.
biological example:
example B1: extra large spodoptera (egyptian cotton leaf worm)
Test compounds transfer pipet to be administered to 24 orifice plates from 10'000ppmDMSO stock solution and to mix with agar.Lactuca sativa seeds to be placed on this agar and to close this porous plate with the flat board that another block also comprises agar.After 7 days, root has been absorbed by this compound and lettuce has grown into lid flat board.Now these lettuce leavess are switched in lid flat board.Noctua ovum is aspirated through the plastic mould on one piece of moist gel marking paper and the flat board closed.After infecting 6 days, relative to untreated samples, for mortality ratio, Antifeeding Effects and growth-inhibiting assessment sample.
Following compound to give in these three classifications (mortality ratio, Antifeeding Effects or growth-inhibiting) effect of at least one at least 80% at 12.5ppm a test rate place:
V20.02, V20.01, V16.02, V12.02, V16.01, V12.01 and V12.03
example B2: extra large spodoptera (egyptian cotton leaf worm):
Agar cotton leaf disk being placed in 24 hole microtiter plates is sprayed with the water-based test soln prepared from 10'000ppmDMSO stock solution.After drying, leaf disk is infected with five L1 phase larvas.After infecting 3 days, for mortality ratio, these samples are assessed.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
Following compound obtains the control of at least 80% under 200ppm rate of application:
V14.01, V12.18, V16.08, V20.02, V16.02, V12.20, V12.02, V16.01, V12.01, V7.11, V12.03, V25.03 and V7.09
example B3: small cabbage moth (Plutellaxylostella) (small cabbage moth (Diamondbackmoth)):
The 24 hole microtiter plates with artificial diet are processed by moving liquid with the water-based test soln prepared from 10'000ppmDMSO stock solution.After drying, with L2 phase larva, each plate is infected (10 to 15/hole).After infecting 5 days, for mortality ratio, these samples are assessed.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
V14.01, V16.08, V20.08, V20.02, V16.09, V16.03, V16.07, V16.02, V12.02, V16.01, V12.01, V7.11, V12.03, V13.05, V25.03 and V7.09
example B4: cucumber strip chrysomelid (corn rootworm):
The 24 hole microtiter plates with artificial diet are processed by moving liquid with the water-based test soln prepared from 10'000ppmDMSO stock solution.After drying, with L2 phase larva, each plate is infected in (6 to 10/ hole).After infecting 5 days, compared to untreated samples, for mortality ratio and growth-inhibiting, sample is assessed.
Following compound to give in two classifications (mortality ratio or growth-inhibiting) effect of at least one at least 80% under 200ppm rate of application:
V14.01, V12.18, V16.08, V20.02, V16.09, V16.03, V16.07, V16.02, V12.20, V12.02, V12.01, V7.11, V12.03, V13.05, V25.03 and V7.09.
example B5: black peach aphid (green peach aphid worm):
Agar Sunflower Leaf disk being placed in 24 hole microtiter plates is sprayed with the water-based test soln prepared from 10'000ppmDMSO stock solution.After drying, the aphid colony of these leaf disk mixed ages is infected.After infecting 6 days, for mortality ratio, these samples are assessed.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
V14.01, V16.08, V20.08, V16.09, V16.03, V16.07, V16.02, V12.20, V12.02, V14.05, V16.01, V12.17, V12.01, V7.11, V12.03, V25.03 and V7.09.
example B6: black peach aphid (green peach aphid worm):
The root of the pea seedling aphid colony being subject to mixed age infected is placed directly in the water-based test soln prepared from 10'000ppmDMSO stock solution.Seedling is placed in test soln after 6 days, for mortality ratio, these samples is assessed.
Following compound obtains the mortality ratio of at least 80% under 24ppm test rate:
V16.08, V20.08, V16.09, V16.03, V16.07, V12.20, V12.02, V14.05, V12.17, V12.01 and V12.03.
example B7: black peach aphid (green peach aphid worm):
Test compounds from 10'000ppmDMSO stock solution to be administered in 24 hole microtiter plates by transfer pipet and to mix with sucrose solution.The Parafilm film that these flat boards stretch is closed.A kind of 24 hole plastic moulds to be seated on this flat board and the pea seedling through infecting directly is seated on this Parafilm film.The flat board gel blots paper (gelblottingpaper) this process infected and other plastic mould are closed, and are then inverted.After infecting 5 days, for mortality ratio, these samples are assessed.
Following compound obtains the mortality ratio of at least 80% under 12ppm a test rate:
V12.20, V12.02, V14.05, V16.01, V12.17, V12.01, V7.11, V12.03 and V7.09
example B8: onion thrips (onion thrips):
Agar Sunflower Leaf disk being placed in 24 hole microtiter plates is sprayed with the water-based test soln prepared from 10'000ppmDMSO stock solution.After drying, the thrips population of these leaf disks with a mixed age is infected.After infecting 6 days, for mortality ratio, these samples are assessed.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
V12.01, V12.03 and V7.09
example B9: Frankliniella occidentalis (western classical architecture):
Agar Sunflower Leaf disk being placed in 24 hole microtiter plates is sprayed with the water-based test soln prepared from 10'000DMSO stock solution.After drying, the flower thrips population of these leaf disks with a mixed age is infected.After infecting 7 days, for mortality ratio, these samples are assessed.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
V12.02
example B10: Bemisia tabaci (cotton aleyrodid):
Agar cotton leaf disk being placed in 24 hole microtiter plates is sprayed with the water-based test soln prepared from 10'000ppmDMSO stock solution.After drying, leaf disk is infected with adult aleyrodid.After hatching 6 days, for mortality ratio, these samples are checked.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
V12.20, V12.02, V12.01, V13.05, V25.03 and V7.09.
example B11: T.urticae Koch (Tetranychus urticae):
Beans leaf disk on agar in the 24 hole microtiter plates water-based test soln prepared from 10'000ppmDMSO stock solution is sprayed.After drying, the mite population of these leaf disks with a mixed age is infected.After infecting 8 days, the mortality ratio for mixed population (flowing platform) is assessed these samples.
Following compound obtains the mortality ratio of at least 80% under 200ppm rate of application:
V14.01, V12.18, V20.08 and V16.02.
example B12: Aedes aegypti (yellow jack mosquito):
Larvacide, contacts/ingests activity, treatment
10 to 15 albopictus larvaes (L2) are placed in 96 hole microtiter plates together with a kind of nutritional blend.By test compounds pipette, extract in this some holes.After hatching 2 day time, for mortality ratio and growth-inhibiting, insect is assessed.
Following compound to give in these two classifications (mortality ratio or growth-inhibiting) effect of at least one at least 80% under 5ppm a test rate:
V12.01
Claims (17)
1. there is a compound for Formula I,
A-B(I)，
Wherein A is a group being selected from lower group, and this group is by chemical formula A
1to A
8composition:
Wherein arrow represents the point being attached to group B; And
B is a group being selected from lower group, and this group is by chemical formula B
1to B
11composition:
Wherein arrow represents the point being attached to group A;
Wherein
L
1methylene radical or a direct key;
V
0nitrogen or CR
5;
V
1nitrogen or CR
20;
V
2nitrogen or CR
21;
V
3nitrogen or CR
22;
V
4nitrogen or CR
23;
V
5nitrogen or CR
24;
V
6nitrogen or CR
25;
V
7nitrogen or CR
26;
V
8nitrogen or CR
27;
V
9nitrogen, or CR
28;
V
10nitrogen or CR
29;
V
11nitrogen or CR
30;
G
1nitrogen or CR
31;
G
2nitrogen or CR
32;
G
3-NR
35, Sauerstoffatom or a sulphur atom;
G
4nitrogen or CR
33;
G
5nitrogen or CR
34;
J
1, J
2, J
3form 5 yuan of heterocycles together, this heterocycle can be saturated or unsaturated, and comprise one or two atom being selected from lower group, this group is made up of nitrogen, oxygen and sulphur, and it is monosubstituted or polysubstituted that this ring can be selected from the substituting group of lower group, and this group is by C
1-C
6alkyl, halogen and or C
1-C
6haloalkyl forms, and its condition is if this ring comprises two Sauerstoffatoms or two sulphur atoms, and they by a carbon atom separately;
R
1and R
2identical or different and each expression hydrogen, halogen, C
1-C
6alkyl or C
1-C
6haloalkyl;
R
3be one and can be selected from the monosubstituted or polysubstituted C of the substituting group of lower group
1-C
6alkyl, C
2-C
6thiazolinyl or C
2-C
6alkynyl group, this group is by C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen, C
3-C
6cycloalkyl forms, described C
3-C
6cycloalkyl itself can be selected from halogen and C
1-C
3the substituting group of alkyl is monosubstituted or polysubstituted; And monosubstituted or polysubstituted by 5-or 6-unit heterocyclic group, it is monosubstituted or polysubstituted that this heterocyclic group can be selected from the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
Or R
3to be selected from the monosubstituted or polysubstituted C of the substituting group of lower group
3-C
6cycloalkyl, this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group and halogen composition;
Or R
3be one and can be selected from monosubstituted or polysubstituted 5-or the 6-unit heterocyclic group of the substituting group of lower group, this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
Or R
3-CO
2r
36,-C (O) R
36or hydrogen;
R
35be hydrogen, the monosubstituted or polysubstituted C of the substituting group of lower group can be selected from
1-C
6alkyl, this group is by C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl forms, described C
3-C
6cycloalkyl itself can be selected from halogen and C
1-C
3the substituting group of alkyl is monosubstituted or polysubstituted; Or its a kind of N-oxide compound;
R
4, R
5, R
20, R
21, R
22, R
23, R
24, R
25, R
26, R
27, R
28, R
29, and R
30be identical or different, and represent cyano group, nitro, halogen, hydroxyl, C
1-C
6alkene oxygen base, C
1-C
6-halogenated alkoxy ,-C (O) R
36or hydrogen; Or
Monosubstituted or the polysubstituted C of the substituting group of lower group can be selected from
1-C
6alkyl, this group is by cyano group, halogen, hydroxyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl forms, and described cycloalkyl itself can be selected from the substituting group replacement of lower group, and this group is by halogen and C
l-C
3alkyl forms; Or represent
One can be selected from the monosubstituted or polysubstituted phenyl group of the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18and R
19be identical or different, and represent C
1-C
6alkyl, C
1-C
6haloalkyl or hydrogen, and group CR in addition
13r
14can be a carbonyl group C=O;
R
31, R
32, R
33and R
34be identical or different, and represent C
1-C
6alkyl, C
1-C
6haloalkyl ,-OR
7,-S (O)
nr
36,-NR
36r
37,-CO
2r
36,-C (O) R
36, cyano group, nitro, halogen or hydrogen;
R
36and R
37be identical or different, and represent hydrogen, the monosubstituted or polysubstituted C of following substituting group can be selected from
1-C
6alkyl: C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
2-C
6alkene oxygen base, C
2-C
6haloalkene oxygen base, C
2-C
6alkynyloxy group, C
2-C
6halo alkynyloxy group, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, cyano group, hydroxyl, halogen and C
3-C
6cycloalkyl, wherein said C
3-C
6it is monosubstituted or polysubstituted that cycloalkyl can be selected from the substituting group of lower group, and this group is by halogen and C
l-C
3alkyl forms; Or
R
36and R
37be identical or different and represent
One can be selected from the monosubstituted or polysubstituted phenyl group of the substituting group of lower group, and this group is by C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6alkyl alkylthio base, C
1-C
6haloalkyl sulfanyl, C
1-C
6alkyl sulphinyl, C
1-C
6alkylsulfinyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6alkyl-carbonyl, C
2-C
6halogenated alkyl carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6halo alkoxy carbonyl, C
1-C
6alkylamino, C
1-C
6haloalkylamino, C
2-C
8dialkyl amido, C
2-C
8halo dialkyl amido, halogen, cyano group and nitro form;
Each m represents 0,1 or 2 independently, and n represents 0,1 or 2, and its condition is:
A) at-S (O)
nr
36in, when n is 0, R
36hydrogen;
If b) B is B1, so A and A2, A3 with A5 are different;
If c) A is A1, so B and B1, B7, B8, B9 are different with B10;
If d) A is A
5, so B is and B
10different;
Together with salt acceptable in agrochemicals, enantiomer, diastereomer, tautomer, and the N-oxide compound of these compounds.
2. the compound with Formula I according to claim 1, is represented by following combination
Group A2 and group B, B is selected from B7, B9 and B11;
Wherein A2 is represented by group A2.1
Wherein R
40halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
G
21nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And
G
51nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And group B 7, B9 and B11 are represented by the group being selected from B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
3. the compound with Formula I according to claim 1, is represented by following combination
Group A3 and group B, B is selected from B7, B9 and B11;
Wherein A3 is represented by group A3.1
Wherein R
47halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
G
41nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And
G
22nitrogen, CH, C-C
1-C
6alkyl, C-C
1-C
6haloalkyl, C-halogen, C-CN, C-O-C
1-C
4alkyl, C-S-C
1-C
4alkyl, C-SO
2-C
1-C
4alkyl, C-S-phenyl, C-SO
2-phenyl or C-SO
2-C
1-C
4haloalkyl; And group B 7, B9 and B11 are represented by the group being selected from B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
4. the compound with Formula I according to claim 1, is represented by following combination
Group A4 and group B 1;
Wherein A4 is represented by group A4.1
Wherein R
48halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
J
3sulphur, oxygen or N-methyl; And
R
49hydrogen, C
1-C
6alkyl, C
1-C
6haloalkyl, halogen, CN, O-C
1-C
4alkyl, S-C
1-C
4alkyl, SO
2-C
1-C
4alkyl, S-phenyl, SO
2-phenyl or SO
2-C
1-C
4haloalkyl;
And group B 1 is
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
5. the compound with Formula I according to claim 1, is represented by following combination
Group A5 and group B, B is selected from B1, B7, B9 and B11;
Wherein A5 is represented by group A5.1
Wherein
G
55nitrogen or C-R
53;
R
53c
1-C
4alkyl;
G
25nitrogen or methyne; And
R
52halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne;
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
6. the compound with Formula I according to claim 1, is represented by following combination
Group A6 and group B, B is selected from B1, B7, B9 and B11;
Wherein A6 is represented by group A6.1
Wherein
G
36n-R
55, oxygen or sulphur;
R
55c
1-C
4alkyl;
G
26nitrogen or methyne; And
R
54halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne,
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
7. the compound with Formula I according to claim 1, is represented by following combination
Group A7 and group B, B is selected from B1, B7, B9 and B11;
Wherein A7 is represented by group A7.1
Wherein
G
57nitrogen or C-R
57;
R
57hydrogen or C
1-C
4alkyl; And
R
56halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne;
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
8. the compound with Formula I according to claim 1, is represented by following combination
Group A8 and group B, B is selected from B1, B7, B9 and B11;
Wherein A8 is preferably represented by group A8.1
Wherein
G
48nitrogen or C-R
59;
R
59hydrogen or C
1-C
4alkyl; And
R
58halogen, C
1-C
4haloalkyl, C
1-C
4halogenated alkylthio, C
1-C
4halogenated alkyl sulfonyl, O (C
1-C
4haloalkyl), SF
5, phenylcarbonyl group sulfenyl, sulfydryl or C
1-C
4alkoxy carbonyl;
And group B 1, B7, B9 and B11 are preferably represented by the group being selected from B1.1, B7.1, B9.1 and B11.1
Wherein m is 0,1 or 2;
R
51c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
50hydrogen, C
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
82nitrogen or methyne;
R
41c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
42c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl;
Wherein m is 0,1 or 2;
V
81nitrogen or methyne;
R
43c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
44c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
Wherein m is 0,1 or 2;
R
45c
1-C
4alkyl, C
1-C
4haloalkyl, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl; And
R
46c
1-C
4alkyl, C
1-C
4haloalkyl, C
1-C
3halogenated alkoxy, C
3-C
6cycloalkyl, C
3-C
6cycloalkyl-C
1-C
4alkyl, C
3-C
6halogenated cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group or C
2-C
6alkynyl.
9. the compound with Formula I according to 1, wherein about each B, L
1it is a direct key.
10. the compound with Formula I according to 1, wherein about each A, R
1identical or different and each expression hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl.
11. compounds with Formula I according to 10, wherein about each A, R
2identical or different and each expression hydrogen, halogen, C
1-C
3alkyl or C
1-C
3haloalkyl.
12. compounds with Formula I according to 10, wherein about each B, R
3identical or different and each expression C
1-C
3alkyl or C
1-C
3haloalkyl.
13. compounds with Formula I according to 10, wherein about each B, R
4identical or different and each expression hydrogen or C
1-C
3alkyl.
14. 1 kinds kill insect, kill mite, nematicide or kill mollusk composition, said composition comprise one kill insect, kill mite, nematicide or kill mollusk significant quantity according to claim 1 there is Formula I compound and a kind of suitable carrier for this compound or thinner.
The method of 15. 1 kinds of antagonism and control harmful organism, the method comprises killing insect, kills mite, nematicide or kill the compound with Formula I according to claim 1 of mollusk significant quantity or a kind of composition comprising the compound with Formula I is applied to harmful organism, place, harmful organism place, or be applied to the plant being subject to pest infestation, except a kind of by operation or therapy for the treatment of except the method for human body or animal body and the diagnostic method implemented human body or animal body.
16. 1 kinds of methods of attacking from harmful organism for the protection of plant propagation material, the method comprises the place of planting with this reproductive material of compositions-treated according to claim 14 or this reproductive material.
17. according to the plant propagation material of the method process described in claim 16.
Priority Applications (2)
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|---|---|---|---|
| CN201480043333.0A CN105431433B (en) | 2013-07-02 | 2014-06-19 | There are two rings or tricyclic heterocyclic with sulfur-bearing substituent for killing harmful organism activity |
| CN201710871364.0A CN107652292B (en) | 2013-07-02 | 2014-06-19 | Pesticidally active bicyclic or tricyclic heterocycles with sulfur-containing substituents |
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|---|---|---|---|
| EP13174698 | 2013-07-02 | ||
| EP13174698.4 | 2013-07-02 | ||
| EP13176263.5 | 2013-07-12 | ||
| EP13176263 | 2013-07-12 | ||
| EP13197069.1 | 2013-12-13 | ||
| EP13197069 | 2013-12-13 | ||
| CNPCT/CN2014/076736 | 2014-05-04 | ||
| CN2014076736 | 2014-05-04 | ||
| CN201480043333.0A CN105431433B (en) | 2013-07-02 | 2014-06-19 | There are two rings or tricyclic heterocyclic with sulfur-bearing substituent for killing harmful organism activity |
| PCT/EP2014/062946 WO2015000715A1 (en) | 2013-07-02 | 2014-06-19 | Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents |
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| CN201710871364.0A Active CN107652292B (en) | 2013-07-02 | 2014-06-19 | Pesticidally active bicyclic or tricyclic heterocycles with sulfur-containing substituents |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106414441A (en) * | 2014-02-17 | 2017-02-15 | 拜耳作物科学股份公司 | 2-(het)aryl-substituted condensed bicyclic heterocycle derivatives as pest control agents |
| CN109996799A (en) * | 2016-08-15 | 2019-07-09 | 拜耳作物科学股份公司 | Fused bicyclic heterocycle derivative as pest control agent |
| CN110198942A (en) * | 2017-01-24 | 2019-09-03 | 住友化学株式会社 | Condensed heterocyclic compouds and composition containing it |
| CN110582498A (en) * | 2017-04-27 | 2019-12-17 | 日本农药株式会社 | Condensed heterocyclic compound or salt thereof, agricultural and horticultural insecticide containing the same, and method of using the same |
| US11413291B2 (en) | 2017-09-18 | 2022-08-16 | Syngenta Participations Ag | Pesticidally active heterocyclic derivatives with sulfur containing substituents |
| CN115135384A (en) * | 2019-11-28 | 2022-09-30 | 日本农药株式会社 | Benzimidazole compound or its salt, and agricultural and horticultural insecticide and acaricide containing the same and method of using the same |
| CN115702149A (en) * | 2020-04-30 | 2023-02-14 | 先正达农作物保护股份公司 | Pesticidally active heterocyclic derivatives with sulfur-containing substituents |
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| WO2013018928A1 (en) * | 2011-08-04 | 2013-02-07 | Sumitomo Chemical Company, Limited | Fused heterocyclic compound and use thereof for pest control |
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| ES8401486A1 (en) * | 1981-11-10 | 1983-12-01 | Wellcome Found | New imidazo[4,5-c]pyridine derivatives, processes for their preparation and pharmaceutical formulations containing such compounds. |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012086848A1 (en) * | 2010-12-24 | 2012-06-28 | Sumitomo Chemical Company, Limited | Fused heterocyclic compound and use for pest control thereof |
| WO2013018928A1 (en) * | 2011-08-04 | 2013-02-07 | Sumitomo Chemical Company, Limited | Fused heterocyclic compound and use thereof for pest control |
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|---|---|---|---|---|
| CN106414441A (en) * | 2014-02-17 | 2017-02-15 | 拜耳作物科学股份公司 | 2-(het)aryl-substituted condensed bicyclic heterocycle derivatives as pest control agents |
| CN109996799A (en) * | 2016-08-15 | 2019-07-09 | 拜耳作物科学股份公司 | Fused bicyclic heterocycle derivative as pest control agent |
| CN109996799B (en) * | 2016-08-15 | 2022-07-19 | 拜耳作物科学股份公司 | Fused bicyclic heterocyclic derivatives as pest control agents |
| CN110198942A (en) * | 2017-01-24 | 2019-09-03 | 住友化学株式会社 | Condensed heterocyclic compouds and composition containing it |
| US11161843B2 (en) | 2017-01-24 | 2021-11-02 | Sumitomo Chemical Company, Limited | Fused heterocyclic compound and composition containing same |
| CN110198942B (en) * | 2017-01-24 | 2022-04-15 | 住友化学株式会社 | Fused heterocyclic compound and composition containing the same |
| CN110582498A (en) * | 2017-04-27 | 2019-12-17 | 日本农药株式会社 | Condensed heterocyclic compound or salt thereof, agricultural and horticultural insecticide containing the same, and method of using the same |
| CN110582498B (en) * | 2017-04-27 | 2022-06-24 | 日本农药株式会社 | Condensed heterocyclic compound or salt thereof, agricultural and horticultural insecticide containing the same, and method of using the same |
| US11413291B2 (en) | 2017-09-18 | 2022-08-16 | Syngenta Participations Ag | Pesticidally active heterocyclic derivatives with sulfur containing substituents |
| CN115135384A (en) * | 2019-11-28 | 2022-09-30 | 日本农药株式会社 | Benzimidazole compound or its salt, and agricultural and horticultural insecticide and acaricide containing the same and method of using the same |
| CN115135384B (en) * | 2019-11-28 | 2024-03-22 | 日本农药株式会社 | Benzimidazole compound or salt thereof, agricultural and horticultural insecticide/acaricide containing the same, and method for using the same |
| CN115702149A (en) * | 2020-04-30 | 2023-02-14 | 先正达农作物保护股份公司 | Pesticidally active heterocyclic derivatives with sulfur-containing substituents |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107652292A (en) | 2018-02-02 |
| CN107652292B (en) | 2020-11-17 |
| CN105431433B (en) | 2018-04-06 |
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