CN1377358A - Novel herbicides - Google Patents
Novel herbicides Download PDFInfo
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- CN1377358A CN1377358A CN00813584A CN00813584A CN1377358A CN 1377358 A CN1377358 A CN 1377358A CN 00813584 A CN00813584 A CN 00813584A CN 00813584 A CN00813584 A CN 00813584A CN 1377358 A CN1377358 A CN 1377358A
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- alkyl
- halogenated
- alkoxy
- substituted
- compound
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-
- 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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/616—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/28—Two oxygen or sulfur atoms
- C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
- C07D231/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to compounds of formula (I), wherein the substituents have the meaning cited in Claim (1). Said compounds are suitable for utilization as herbicides.
Description
The present invention relates to newly, have the pyrazolone derivative of weeding activity, their preparation method contains the composition of above-claimed cpd, and controlling weeds, particularly prevents and treats the weeds that grow in useful crop, or suppresses the purposes of plant-growth.
Pyrazolone derivative with weeding activity is disclosed in, for example among WO92/16510 and the WO96/21652.
Found at present newly, had weeding and suppress the 4-arylpyrazole quinoline ketone of growth activity.
Therefore the present invention relates to formula I compound
Wherein
R
1And R
3Be hydrogen independently of one another, halogen, nitro, cyano group, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, three (C
1-C
4The alkyl silyl)-C
2-C
4Alkynyl, C
1-C
4Haloalkyl, C
2-C
6Halogenated alkenyl, C
3-C
6Cycloalkyl, halo C
3-C
6Cycloalkyl, benzyl, C
2-C
6Alkoxyalkyl, C
2-C
6Alkylthio alkyl, hydroxyl, sulfydryl, C
1-C
6Alkoxyl group, C
3-C
6Alkenyloxy, C
3-C
6Alkynyloxy group, C
1-C
4Alkyl-carbonyl, C
1-C
4Alkoxy carbonyl, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, amino, C
1-C
4Alkylamino, two (C
1-C
4Alkyl) amino, C
1-C
4Hydroxyalkyl, formyl radical, C
1-C
4Alkyl-carbonyl-amino or C
1-C
4Alkyl sulfonyl-amino,
R
2Be phenyl, naphthyl maybe can contain 1 or 2 and be selected from nitrogen, the heteroatomic 5-of oxygen and sulphur or 6-unit aromatic ring, and phenyl ring, naphthalene nucleus and 5-or 6-unit aromatic ring can be by halogens, C
3-C
8Cycloalkyl, hydroxyl, sulfydryl, amino, amino-C
1-C
6Alkyl, carboxyl-C
1-C
6Alkyl, cyano group, nitro or formyl radical replace; And/or
Phenyl ring, naphthalene nucleus and 5-or 6-unit aromatic ring can be by C
1-C
6Alkyl, C
1-C
6Alkoxyl group, hydroxyl-C
1-C
6Alkyl, C
1-C
6Alkoxy-C
1-C
6Alkyl, C
1-C
6Alkoxy-C
1-C
6Alkoxyl group, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkylthio, C
1-C
6Alkyl sulphinyl, C
1-C
6Alkyl sulphonyl, one-C
1-C
6Alkylamino, two-C
1-C
6Alkylamino, C
1-C
6Alkyl-carbonyl-amino, C
1-C
6Alkyl-carbonyl-(C
1-C
6Alkyl) amino, C
2-C
6Alkenyl, C
3-C
6Alkenyloxy, hydroxyl-C
3-C
6Alkenyl, C
1-C
6Alkoxy-C
3-C
6Alkenyl, C
1-C
6Alkoxy-C
3-C
6Alkenyloxy, C
2-C
6Alkenyl carbonyl, C
2-C
6Alkenyl thio, C
2-C
6The alkenyl sulfinyl, C
2-C
6The alkenyl alkylsulfonyl, one or two-C
2-C
6Alkenyl amino, C
1-C
6Alkyl-(C
3-C
6Alkenyl) amino, C
2-C
6Alkenyl carbonyl amino, C
2-C
6Alkenyl carbonyl-(C
1-C
6Alkyl) amino, C
2-C
6Alkynyl, C
3-C
6Alkynyloxy group, hydroxyl-C
3-C
6Alkynyl, C
1-C
6Alkoxy-C
3-C
6Alkynyl, C
1-C
6Alkoxy-C
4-C
6-alkynyloxy group, C
2-C
6The alkynyl carbonyl, C
2-C
6The alkynes sulfenyl, C
2-C
6The alkynyl sulfinyl, C
2-C
6The alkynyl alkylsulfonyl, one-or two-C
3-C
6Alkynyl amino, C
1-C
6Alkyl-(C
3-C
6Alkynyl) amino, C
2-C
6Alkynyl carbonylamino or C
2-C
6Alkynyl carbonyl-(C
1-C
6Alkyl) the amino replacement; And/or
Phenyl ring, naphthalene nucleus and 5-or 6-unit aromatic ring can be by halo C
1-C
6Alkyl, halo C
1-C
6Alkoxyl group, halogenated hydroxyl-C
1-C
6Alkyl, halo C
1-C
6Alkoxy-C
1-C
6Alkyl, halo C
1-C
6Alkoxy-C
1-C
6Alkoxyl group, halo C
1-C
6Alkyl-carbonyl, halo C
1-C
6Alkylthio, halo C
1-C
6Alkyl sulphinyl, halo C
1-C
6Alkyl sulphonyl, halo one-C
1-C
6Alkylamino, halo two-C
1-C
6Alkylamino, halo C
1-C
6Alkyl-carbonyl-amino, halo C
1-C
6Alkyl-carbonyl-(C
1-C
6Alkyl) amino, halo C
2-C
6Alkenyl, halo C
3-C
6Alkenyloxy, halogenated hydroxyl-C
3-C
6Alkenyl, halo C
1-C
6Alkoxy-C
2-C
6Alkenyl, halo C
1-C
6Alkoxy-C
3-C
6Alkenyloxy, halo C
2-C
6Alkenyl carbonyl, halo C
2-C
6Alkenyl thio, halo C
2-C
6The alkenyl sulfinyl, halo C
2-C
6The alkenyl alkylsulfonyl, halo one or two-C
3-C
6Alkenyl amino, halo C
1-C
6Alkyl-(C
3-C
6Alkenyl) amino, halo C
2-C
6Alkenyl carbonyl amino, halo C
2-C
6Alkenyl carbonyl-(C
1-C
6Alkyl) amino, halo C
2-C
6Alkynyl, halo C
3-C
6Alkynyloxy group, halogenated hydroxyl-C
3-C
6Alkynyl, halo C
1-C
6Alkoxy-C
3-C
6Alkynyl, halo C
1-C
6Alkoxy-C
4-C
6-alkynyloxy group, halo C
2-C
6The alkynyl carbonyl, halo C
2-C
6The alkynes sulfenyl, halo C
2-C
6The alkynyl sulfinyl, halo C
2-C
6The alkynyl alkylsulfonyl, halo one-or two-C
3-C
6Alkynyl amino, halo C
1-C
6Alkyl-(C
3-C
6Alkynyl) amino, halo C
2-C
6Alkynyl carbonylamino or by halo C
2-C
6Alkynyl carbonyl-(C
1-C
6Alkyl) the amino replacement; And/or
Phenyl ring, naphthalene nucleus and 5-or 6-unit aromatic ring can be COOR by structural formula
50, CONR
51, SO
2NR
53R
54Or SO
2OR
55Group replace R wherein
50, R
51, R
52, R
53, R
54And R
55Be hydrogen independently of one another, C
1-C
6Alkyl, C
2-C
6Alkenyl or C
3-C
6Alkynyl, or be the C that is replaced by halogen, hydroxyl, alkoxyl group, sulfydryl, amino, cyano group, nitro, alkylthio, alkyl sulphinyl or alkyl sulphonyl separately
1-C
6Alkyl, C
2-C
6Alkenyl or C
3-C
6Alkynyl,
R
4And R
5Be hydrogen independently of one another, C
1-C
12Alkyl, C
1-C
12Haloalkyl, C
1-C
12Hydroxyalkyl, C
3-C
8Alkenyl, C
3-C
8Alkynyl, C
1-C
10Alkoxy-C
1-C
8Alkyl, or contain the C of one or two Sauerstoffatom
3-C
8Alkyl, C
1-C
10Alkylthio-C
1-C
8Alkyl, C
3-C
8Cycloalkyl contains 1 or 2 heteroatomic C that is selected from oxygen and sulphur
3-C
8Cycloalkyl, C
3-C
8Halogenated cycloalkyl contains 1 or 2 heteroatomic C that is selected from oxygen and sulphur
3-C
8Halogenated cycloalkyl, phenyl, or by halogen, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6The phenyl that halogenated alkoxy, nitro or cyano group replace, or R
4And R
5Be can contain to be selected from oxygen independently of one another, the heteroatomic 5-of sulphur and nitrogen or 6-unit ring, or
R
4And R
5Atom with their bondings forms 5-to 8-unit ring, and this 5-to 8-unit ring can contain 1 or 2 Sauerstoffatom, sulphur atom or NR
6Group, wherein R
6Be hydrogen, C
1-C
4Alkyl, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkyl sulphonyl, C
3-C
6Alkenyl or C
3-C
6Alkynyl, and above-mentioned 5-to 8-unit ring can be by halogen, hydroxyl, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, C
1-C
10Haloalkyl, C
3-C
8Cycloalkyl, phenyl or benzyl replace; Or
The first ring of above-mentioned 5-to 8-can be replaced by phenyl, and wherein phenyl is again by halogen, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
3-C
6Cycloalkyl, hydroxyl, C
1-C
6Alkoxyl group, C
1-C
6Alkoxy-C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy or nitro replace, or above-mentioned 5-to 8-unit ring replaced by benzyl, and wherein benzyl is again by halogen, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
3-C
6Cycloalkyl, hydroxyl, C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy or nitro replace; Or
The first ring of above-mentioned 5-to 8-can be by CH
2-heteroaryl replaces, and wherein aryl moiety is 5 or 6 yuan, or by with halogen-, C
1-C
6Alkyl-, C
1-C
6Haloalkyl-, C
1-C
6Cycloalkyl-, hydroxyl-, C
1-C
6Alkoxyl group-, C
1-C
6Halogenated alkoxy-or the CH of nitro-replacement
2-heteroaryl replaces, and wherein aryl moiety is 5 or 6 yuan; Or
Above-mentioned 5-to 8-unit ring can be replaced by heteroaryl, and wherein aryl moiety is 5 or 6 yuan, or use by halogen-, C
1-C
6Alkyl-, C
1-C
6Haloalkyl-, hydroxyl-, C
1-C
6Alkoxyl group-, C
1-C
6Halogenated alkoxy-, cycloalkyl-or the heteroaryl of nitro-replacement replace, wherein aryl moiety is 5 or 6 yuan; And
Above-mentioned 5-to 8-unit ring can have and contain condensing or the alkylidene group or the alkylene group chain of spiral shell bonding of 2-6 carbon atom, and this chain can be by oxygen or sulphur atom interruption,
G is a hydrogen ,-C (X
1)-R
30,-C (X
2)-X
3-R
31,-C (X
4)-N (R
32)-R
33,-SO
2-R
34, alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation ,-P (X
5) (R
35)-R
36Or-CH
2X
6C (X
7)-R
37,-CH
2X
8C (X
9)-X
10-R
38,-CH
2X
11C (X
12)-N (R
39)-R
40Or-CH
2X
13SO
2-R
41, X wherein
1, X
2, X
3, X
4, X
5, X
6, X
7, X
8, X
9, X
10, X
11, X
12And X
13Be oxygen or sulphur independently of one another, and R
30, R
31, R
32, R
33, R
34, R
35, R
36, R
37, R
38, R
39, R
40And R
41Be hydrogen independently of one another, C
1-C
12Alkyl or by halogen, formyl radical, cyano group, nitro, three-C
1-C
6Alkyl silyl, hydroxyl, C
1-C
6Alkoxyl group, C
1-C
6Alkoxy carbonyl, amino, C
1-C
6Alkylamino, two-C
1-C
6Alkylamino, sulfydryl, C
1-C
6Alkylthio, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkyl-carbonyl-amino, C
1-C
6Alkoxycarbonyl amino, C
1-C
6Alkyl amino-carbonyl amino, C
1-C
6Alkylthio carbonyl oxygen base, C
1-C
6Alkylthio carbonylamino, C
1-C
6Alcoxyl thiocarbonyl group, thiocarbamoyl, C
1-C
6Alkylthio carbonyl oxygen base, C
1-C
6Alkylthio carbonylamino, C
1-C
6Alkoxyl group thiocarbonyl group amino, C
1-C
6Alkyl sulphinyl, C
1-C
6Alkyl sulphonyl, C
1-C
6Alkylsulfonyloxy, C
1-C
6Alkyl sulfonyl-amino, C
1-C
6The C that Alkoximino, oximino, heteroaryl, benzyloxy, phenoxy group or halogenated phenoxy replace
1-C
12Alkyl; Or
C
2-C
12Alkenyl, C
3-C
12Cycloalkyl is by halogen, C
1-C
6Haloalkyl, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkylthio, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkylamino, C
1-C
6Alkyl-carbonyl-amino, three-C
1-C
6Alkyl silyl or three-C
1-C
6The C that alkyl siloxy replaces
3-C
8Cycloalkyl; Phenyl or alkoxy, halogen, C
1-C
6Haloalkyl, nitro, cyano group, C
1-C
6Alkyl, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkylthio, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkylamino, C
1-C
6Alkyl-carbonyl-amino, three-C
1-C
6Alkyl silyl or three-C
1-C
6The phenyl that alkyl siloxy replaces; Heteroaryl or by halogen, C
1-C
6Haloalkyl, nitro, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkylthio, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkylamino, C
1-C
6Alkyl-carbonyl-amino, three-C
1-C
6Alkyl silyl or three-C
1-C
6The heteroaryl that alkyl siloxy replaces; And
R
34Can also be C
2-C
20Alkenyl or by halogen, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkylthio carbonyl, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkyl sulphonyl, C
1-C
6Alkyl sulphinyl, C
1-C
6Alkyl amino sulfonyl, two-C
1-C
6Alkyl amino sulfonyl, C
1-C
6Alkylsulfonyloxy, C
1-C
6Alkyl sulfonyl amino, C
1-C
6Alkylamino, two-C
1-C
6Alkylamino, C
1-C
6Alkyl carbonyl amino, two-C
1-C
6Alkyl carbonyl amino, cyano group, C
3-C
8Cycloalkyl, C
3-C
8Heterocyclic radical, three-C
1-C
6Alkyl silyl, three-C
1-C
6The C that the heteroaryl of the phenyl of alkyl siloxy, phenyl, replacement, heteroaryl or replacement replaces
2-C
20Alkenyl; Or
C
2-C
20Alkynyl or by halogen, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkylthio carbonyl, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkyl sulphonyl, C
1-C
6Alkyl sulphinyl, C
1-C
6Alkyl amino sulfonyl, two-C
1-C
6Alkyl amino sulfonyl, C
1-C
6Alkylsulfonyloxy, C
1-C
6Alkyl sulfonyl amino, C
1-C
6Alkylamino, two-C
1-C
6Alkylamino, C
1-C
6Alkyl carbonyl amino, two-C
1-C
6Alkyl carbonyl amino, cyano group, C
3-C
7Cycloalkyl, C
3-C
7Heterocyclic radical, three-C
1-C
6Alkyl silyl, three-C
1-C
6The C that the heteroaryl of the phenyl of alkyl siloxy, phenyl, replacement, heteroaryl or replacement replaces
2-C
20Alkynyl; Or
C
3-C
8Cycloalkyl or by halogen, C
1-C
6Haloalkyl, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkylthio, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkylamino, C
1-C
6Alkyl-carbonyl-amino, three-C
1-C
6Alkyl silyl or three-C
1-C
6The C that alkyl siloxy replaces
3-C
8Cycloalkyl; Or
Heteroaryl or by halogen, C
1-C
6Haloalkyl, nitro, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkylthio, C
1-C
6Alkyl oxycarbonyl sulfenyl, C
1-C
6Alkylamino, C
1-C
6Alkyl-carbonyl-amino, three-C
1-C
6Alkyl silyl or three-C
1-C
6The heteroaryl that alkyl siloxy replaces; Or
Heteroaryloxy, the heteroaryloxy of replacement, heteroarylthio, the heteroarylthio that replaces, assorted virtue is amino, and the assorted virtue of replacement is amino, two assorted virtues are amino, and two assorted virtues of replacement are amino, phenyl amino, the phenyl amino that replaces, diphenyl amino, the diphenyl amino of replacement, cycloalkyl amino, the cycloalkyl amino of replacement, bicyclic alkyl amino, the bicyclic alkyl amino that replaces, the cycloalkyloxy of cycloalkyloxy or replacement
And the salt and the diastereomer of formula I compound.
The alkyl that occurs in the substituting group definition can be straight or branched and for example be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group and hexyl and branched chain isomer thereof.Alkenyl and alkynyl and alkoxyl group and the alkylthio that is fit to and other group that contains alkyl unit all are by the abovementioned alkyl deutero-.The example of the cycloalkyl that the present invention is fit to is a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.The preferred fluorine of halogenic substituent, chlorine or bromine.The example that contains heteroatomic 5-and 6-unit aromatic ring is a thienyl, furyl and pyridyl.5-to 8-unit heteroaryl and Heterocyclylalkyl can be, pyrazolidine for example, 1,2,3,6-tetrahydro pyridazine, hexahydro-pyridazine, 1,4,5-Evil diaza alkane, 1,4,5-thiophene diaza alkane and 1,4,5-oxadiazole alkane.
The invention still further relates to formula I compound preferably with amine, basic metal and alkaline earth metal alkali or the salt that forms with quaternary ammonium salt and base.The salt resultant that is fit to for example is disclosed among the WO98/41089.
The invention still further relates to formula I compound and amine, basic metal and alkaline earth metal alkali or the salt that forms with quaternary ammonium salt and base.
In the basic metal and alkaline earth metal hydroxides as the salt resultant, what mention especially is lithium, sodium, potassium, the oxyhydroxide of magnesium or calcium, but the oxyhydroxide of sodium or potassium particularly.
Example as being applicable to the amine that generates ammonium salt is contemplated that ammonia and the primary, secondary and uncle C
1-C
18Alkylamine, C
1-C
4Hydroxyalkyl amine and C
2-C
4Alkoxyalkyl amine, methylamine for example, ethamine, n-propyl amine, isopropylamine, 4 kinds of isomer of butylamine, n-amylamine, isobutylcarbylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, pentadecyl amine, cetylamine, heptadecylamine (HDA), octadecane amine, methyl ethyl-amine, methyl isopropyl amine, tuaminoheptane, the methyl nonyl amine, methyl pentadecyl amine, methyl octadecane amine, ethyl butyl amine, ethyl heptyl amice, the ethyl octylame, hexyl heptyl amice, hexyl octylame, dimethylamine, diethylamine, di-n-propyl amine, Diisopropylamine, Di-n-Butyl Amine, two n-amylamines, di-iso-amylamine, dihexylamine, two heptyl amices, Di-Octyl amine, thanomin, n-propyl alcohol amine, Yi Bingchunan, N, the N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butene base-2-amine, positive amylene-2-amine, 2,3-neohexene-2-amine, dibutene-2-amine, n-hexylene-2-amine, propylene diamine, Trimethylamine 99, triethylamine, three-Tri N-Propyl Amine, tri-isopropyl amine, three-n-Butyl Amine 99, three-isobutylamine, three-sec-butylamine, three-n-amylamine, methoxyethyl amine and ethoxy ethyl amine; Heterocyclic amine, pyridine for example, quinoline, isoquinoline 99.9, morpholine, piperidines, tetramethyleneimine, indoline, rubane and azatropylidene; Uncle's arylamines, as aniline, anisidine, phenetidine, adjacent-,-and para-totuidine, phenylenediamine, p-diaminodiphenyl, naphthylamines and neighbour-,-and right-chloroaniline; But particularly triethylamine, Isopropylamine and Diisopropylamine.
Be applicable to and give birth to salifiable preferred quaternary ammonium hydroxide, for example corresponding to structural formula [N (R
aR
bR
cR
d)] OH, wherein R
a, R
b, R
cAnd R
dBe C independently of one another
1-C
4Alkyl.Other is fit to has other anionic tetraalkyl ammonium base and for example can obtain by anion exchange reaction.
Preferred formula I compound is those compounds, wherein R
1And R
3Be C independently of one another
1-C
4Alkyl, particularly methyl or ethyl, C
2-C
4Alkynyl, particularly ethynyl, C
1-C
6Alkoxyl group, particularly methoxyl group, C
1-C
4Alkylthio, particularly methylthio group, C
1-C
4Haloalkyl, particularly chloromethyl and chloroethyl, formyl radical, C
1-C
4Alkyl-carbonyl, particularly ethanoyl, or C
1-C
4Alkylamino or two (C
1-C
4) alkylamino.Especially preferably methyl, ethyl, ethynyl and methoxyl group.
Another is organized in the preferred formula I compound, R
2Be phenyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, and preferred especially phenyl.The also preferred corresponding ring system that replaces, above-mentioned ring system has halogen, hydroxyl, sulfydryl, amino, cyano group, nitro, formyl radical, C
1-C
6Alkyl, C
1-C
6Haloalkyl and C
3-C
8Cycloalkyl is as substituting group.
Other preferred formula I compound is those compounds, wherein R
4And R
5Be C independently of one another
1-C
12Alkyl, C
1-C
10Alkoxy-C
1-C
8Alkyl or contain the C of 1 or 2 Sauerstoffatom
3-C
8Alkyl, or R
4And R
5With the atom that they connect, form saturated 5-to 8-unit, particularly 6-or 7-unit ring.Preferred especially R
4And R
5Form group-CH together
2CH
2-O-CH
2CH
2-or-(CH
2)
4-, above-mentioned group can be by C
1-C
10Alkyl, C
1-C
10Alkoxyl group, C
1-C
6Alkoxy-C
1-C
6Alkoxyl group or hydroxyl replace and have alkylidene group or the alkylene group chain that contains 2-6 carbon atom, and this chain can be interrupted by oxygen.
Be hydrogen or COR as substituting group G in the also preferred formula I compound
30, pivalyl particularly, C (O) X
3R
31Or SO
2R
34, X wherein
3Be oxygen or sulphur, R
31Be C
1-C
12Alkyl, C
1-C
12Haloalkyl, C
2-C
12Alkenyl, C
1-C
12Alkoxyalkyl, C
3-C
12Cycloalkyl or phenyl, and R
34Be C
1-C
6Alkyl, C
1-C
6Haloalkyl, phenyl, by chloro-, cyano group-or methyl substituted phenyl; Or heteroaryl or by chloro-, cyano group-or methyl substituted heteroaryl.
In other preferred formula I compounds, R
1And R
3Be C independently of one another
1-C
4Alkyl, particularly methyl or ethyl, C
2-C
4Alkynyl, particularly ethynyl, C
1-C
6Alkoxyl group, particularly methoxyl group, or C
1-C
4Alkylthio, particularly methylthio group, R
2Be phenyl, 2-thienyl, 3-thienyl, 2-furyl or 3-furyl, R
4And R
5Be C independently of one another
1-C
12Alkyl, or R
4And R
5Atom with they connect forms group-CH
2CH
2-O-CH
2CH
2-or-(CH
2)
4-, above-mentioned group can be by C
1-C
10Alkyl replaces, and G is hydrogen or COR
30, particularly pivalyl, or C (O) X
3R
31, X wherein
3Be oxygen and R
31Be C
1-C
12Alkyl, C
3-C
12Cycloalkyl or phenyl.
Formula I compound can prepare by currently known methods, and disclosed method in WO97/02243 or the following incorporated by reference document for example is as by the aromatics tin compound, phenyl-trialkyl tin compound (Stille, J.K.Angew.Chem.Int.Ed.Engl.1986,25 for example, 508.Kwon, H.B.; McKee, B.H.; Stille, J.K.J.Org.Chem.1990,55,3114), or zn cpds, as phenyl-zinc halide (Negishi, E.; Valente, L.F.; Kobayashi, M.J.Am.Chem.Soc.1980.102,3298.Knochel, P.; Singer, R.Chem.Rev.1993,93,2117), or aromatics boric acid, as furyl-boric acid (Miyaura, N.; Yanagi, T.; Suzuki, A.Synth.Commun.1981,11,513), or aromatic borate, as phenyl-boric acid dialkyl (Sato, M.; Miyaura, N.; Suzuki, A.Chem.Lett.1989,1405.Watanabe, T.; Miyaura, N.; Suzuki, A.Synlett 1992,3, and 207), or the aromatics Grignard compound, as phenyl-magnesium bromide (Jendrella, H.; Chen, I.J., Synthesis 1990,827; Widdowson, D.A.; Zhang, Y.Z., Tetrahedron 1986,42, and 2111) carry out Pd (O)-catalytic cross-coupling reaction importing aromatic ring R with halogen compounds II (Hal=chlorine, bromine or iodine)
2
Formula II compound can be similar among the WO97/02243 disclosed method preparation or, for example according to following proposal preparation, R among the formula II
1, R
2=CH
2CH
3(Hal=Cl, Br, I).
(II is R wherein for example can to prepare corresponding dimethyl compound according to following proposal
1, R
2=CH
3):
Another preparation method of The compounds of this invention is the hydrazine III coupling with malonic ester IV or Malonamide V and replacement.R
7To R
10Can be hydrogen and/or alkyl, particularly C
1-C
6Alkyl, and/or aryl, preferred phenyl and naphthyl.
For example prepare malonic ester IV or Malonamide V by Pd (O)-catalytic cross-coupling reaction according to following proposal:
According to aforesaid method (Hal
1=Br or I) carry out the Suzuki of VI, Stille or Negishi linked reaction are to generate VII; Diazotization and Sandmeyer reaction (Vogel ' s Textbook ofPractical Organic Chemistry, 5
ThEdition, B.S.Furniss, A.J.Hannaford, P.W.G.Smith, A.R.Tatchell; Longman Scientific ﹠amp; 1989,923 pages of Technical) obtain halogen compounds VIII (Hal
2=Cl, Br or I), this compound can be converted into phenylmalonic acid ester IV (Kawatsura, M. by Pd (O) cross-coupling reaction; Hartwig, J.F.J.Am.Chem.Soc.1999,121,1473).Originate in VIII, be similar to Pd (O) cross-coupling reaction method and obtain propane dinitrile IX, can obtain acid amides V thus.
Also can be by following method preparation I compound, wherein G is a hydrogen, is about to formula XXX compound
Wherein R4 and R5 as above define, with formula VIII compound
R wherein
1, R
2And R
3Described and Hal is a chlorine suc as formula I, and under 30-250 ℃, there is inert solvent in bromine or iodine, reacts under the condition of alkali and palladium catalyst.Preferred reaction is carried out under atmosphere of inert gases.
Formula XXX compound is knownly maybe can prepare by currently known methods, for example, and by J.Chem.Soc.Perkin Trans.1 (1987), (4), disclosed method among the 877-884.Formula VIII compound, for example according to currently known methods, promptly by the aniline of corresponding formula VI by diazonium salt according to for example Sandmeyer prepared in reaction
R wherein
1And R
3Define suc as formula I.Above-mentioned reaction for example is disclosed in Vogel ' s Textbook ofPractical Organic Chemistry, 5
ThEdition, B.S.Furniss, A.J.Hannaford, P.W.G.Smith, A.R.Tatchell; Longman Scientific ﹠amp; Among 1989, the 923 pages of the Technical.Formula VI compound is known, some of them be can buy on the market or they can be similar the known compound preparation.
Be suitable for the alkali of above-mentioned reaction, as three alkali metal phosphates, basic metal and alkaline earth metal hydride, basic metal and alkaline-earth metal aminate or alkali metal alcoholate, Tripotassium phosphate for example, sodium hydride, diisopropylaminoethyl lithium (LDA), sodium tert-butoxide or potassium tert.-butoxide.Special preferred tertiary sodium butylate, potassium tert.-butoxide and Tripotassium phosphate.
The solvent that is fit to is, for example, aromatic hydrocarbon such as dimethylbenzene or toluene, ether such as tetrahydrofuran (THF) diox or glycol dimethyl ether, dimethyl sulfoxide (DMSO) or teritary amide are as dimethyl formamide, N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE or acyclic urea, as N, N '-dimethyl allene urea.
The palladium catalyst that is suitable for the C-C keyed jointing reaction of formula XXX compound and formula VIII compound is generally palladium (II) or palladium (O) complex compound, as dihalide palladium (II), acid chloride (II), palladous sulfate (II), two (triphenylphosphine) palladium chloride (II), two (three cyclopentyl phosphines) palladium chloride (II), two (tricyclohexyl phosphine) palladium chloride (II), two (dibenzalacetone) palladium (O) or tetrakis triphenylphosphine palladium (O).Also can prepare palladium catalyst by palladium (II) or palladium (O) compound and the complexing of required part original position, palladium (II) salt that for example will complexing is as palladium chloride (II) (PdCl
2) or acid chloride (II) (Pd (OAc)
2), with required part, triphenylphosphine (PPh for example
3), three cyclopentyl phosphine or tricyclohexyl phosphines, and the solvent of selecting, formula VIII compound, formula XXX compound and alkali put together.Bidentate ligand also is fit to, for example 1,1 '-two (diphenylphosphine)-ferrocene or 1, two (diphenylphosphine) ethane of 2-.By the reacting by heating mixture, original position generates required palladium (II) or palladium (O) complex compound of C-C linked reaction, and above-mentioned then complex compound causes the C-C linked reaction.
In formula VIII compound, the usage quantity of palladium catalyst is 0.001-50 mole %, and preferable amount is 0.1-15 mole %.
According to the solvent that uses and optional according to pressure selective reaction temperature.Preferred reaction is under atmospheric pressure carried out.Another synthetic method relates to the ortho position functionalization of aryl-linking compound: in this method, attention be at the second ortho-substituent (R
3) the preceding any ortho position CH that exists of introducing
2Must be protected to prevent competitive metallizing.
Formula If type compound can generate by forming aminal (aminal) cyclisation with aldehyde (being formaldehyde) herein.Ic is by hydrazine alcohol, and for example IIIa obtains with the IV reaction.
The intermediate of use and specially designed for this reason following formula XIX in above-mentioned synthetic method is new and also constituted a part of the present invention:
R wherein
0Be COOR
7, COOR
8, CONR
7R
9, CONR
8R
10Or cyano group, and R
00Be hydrogen, COOR
7, COOR
8, CONR
7R
9, CONR
8R
10Or cyano group, and R
7, R
8, R
9And R
10And R
1, R
2And R
3Be as above to define, but R
1And R
3Be not hydrogen simultaneously.
Preferred intermediate is corresponding to following structural
Wherein substituting group as above defines.
In above-mentioned synthetic method, use and the VIII intermediate of specially designed following formula for this reason, be new and also constituted a part of the present invention:
R wherein
1, R
2And R
3As above definition, and Hal is a chlorine, and bromine or iodine is worked as R
1And R
3Be methyl and R
2Hal is not an iodine when being phenyl.
The required hydrazine compound of The compounds of this invention prepares according to a kind of novel method.Therefore this method also constitutes a part of the present invention.The method is characterized in that final step be in absolute alcohol directly with anhydrous haloid acid or with the haloid acid of in-situ preparing, for example the haloid acid for preparing of methyl alcohol and excess acetyl chloride reacts.
Preferably with absolute alcohol such as methyl alcohol and carboxylic acid halides such as acetyl halide, prepared in reaction haloid acid in position, and this is preferred.Preferred haloid acid is a hydrochloric acid.
By formula I compound and organic or inorganic acid are being removed water or are being existed under the condition of coupling reagent reaction to introduce substituting group G.Chloride of acid and acid anhydrides also are applicable to above-mentioned purpose.Should be noted in the discussion above that according to substituent R
1, R
3, R
4And R
5-R
10Type, formula I compound can how much and/or the form of mixture of optical isomers form or tautomerism mixture exist.When G=H, for example Compound I can be used as following three kinds of balance tautomers existence.
Therefore, work as R
4R
5The time, the introducing of G can generate two other geometrical isomer:
The reaction of production I compound is preferably having inert to proton, carries out in the inert organic solvents.Above-mentioned solvent is a hydrocarbon, as benzene, and toluene, dimethylbenzene or hexanaphthene, hydrochloric ether is as methylene dichloride, trichloromethane, tetrachloromethane or chlorobenzene, ether such as diethyl ether, glycol dimethyl ether, diglyme, tetrahydrofuran (THF) Huo diox, nitrile such as acetonitrile or propionitrile, acid amides such as N, dinethylformamide, diethylformamide or N-Methyl pyrrolidone.Preferable reaction temperature is-20 ℃ to+120 ℃.General reaction slight exotherm is also at room temperature carried out usually.Be to reduce the reaction times or promote reaction, also selectively short period of time reacting by heating mixture to boiling point.Also can by add several alkali as catalysts to shorten the reaction times.The alkali that is fit to is tertiary amine particularly, Trimethylamine 99 for example, triethylamine, rubane, 1,4-diazabicylo [2.2.2] octane, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene or 1,5-diazabicylo [5.4.0] 11 carbon-7-alkene.Yet can also use mineral alkali as alkali, hydride for example, as sodium hydride or hydrolith, oxyhydroxide such as sodium hydroxide or potassium hydroxide, carbonate such as yellow soda ash and salt of wormwood, or supercarbonate such as sodium bicarbonate and saleratus.By concentrating and/or evaporating solvent separation and recrystallization or grinding purifying by be difficult to solid residue in the dissolved solvent therein at resistates, solvent is ether for example, aromatic hydrocarbons or hydrochloric ether with ordinary method for formula I compound.
When using formula I compound of the present invention or containing their composition, any conventional application process all is fit on the agricultural, and as preemergence application, postemergence application and seed dressing, and the whole bag of tricks and technology are as the sustained release of activeconstituents.In the aforesaid method, activeconstituents is applied to mineral grain carrier or aggregated particles (urea/formaldehyde) and dry with solution.As being fit to, can also use dressing (coated granule), it can make activeconstituents quantitatively discharge in specified time.
Formula I compound can former medicine form, it is the former medicinal weedicide of doing that chemosynthesis obtains, but preferably the conventional auxiliary agent that uses in preparation process is in a usual manner made preparation, for example make missible oil, directly spray or diluting soln the emulsion of dilution, wettable powder, soluble powder, pulvis, granule and microcapsule.Above-mentioned preparation is disclosed in, for example the 9-13 page or leaf of WO97/34485.As the character of composition, select application process according to intended purposes and main environmental conditions, as spraying, atomizing is dusted, and is moistening, broadcasts sowing or bold and vigorous watering.
Preparation, promptly contain formula I activeconstituents or at least a formula I activeconstituents and one or more solids used always or the composition of liquid adjuvants, preparaton or mixture can prepare by currently known methods, for example with activeconstituents and auxiliary agent, for example solvent or solid carrier thorough mixing and/or grinding.Can when the preparation preparation, use surface active cpd (tensio-active agent) in addition.The example of solvent and solid carrier for example is disclosed in the 6th page of WO97/34485.
Be processed into the character of the formula I activeconstituents of preparation according to need, suitable surface active cpd is to have well emulsify, disperses and the nonionic of wet characteristic positively charged ion and/or anion surfactant and surfactant mixture thereof.
The negatively charged ion that is fit to, the example of nonionic and cats product is listed in, for example, in WO97/34485 the 7th and 8 pages.The tensio-active agent of using always in the preparation process, be disclosed in " Mc Cutcheon ' s Detergents and Emulsifiers Annual " MC PublishingCorp. especially, Ridgewood New Jersey, 1981, Stache, H., " Tensid-Taschenbuch ", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J.Ash, " Encyclopedia of Surfactants ", I-III volume, Chemical PublishingCo., New York, the tensio-active agent among the 1980-81 also are applicable to herbicidal composition preparation of the present invention.
Usually contain 0.1-99% weight in the herbicidal formulations, the weedicide of 0.1-95% weight particularly, 1-99.9% weight, the particularly solid of 5-99.8% weight or liquid adjuvants and 0-25% weight, the particularly tensio-active agent of 0.1-25% weight.Yet the preferred concentrate formulation in commercially available prod, the end user uses the dilution preparation usually.Also can comprise other composition such as stablizer in the composition, for example vegetables oil and epoxidised vegetables oil (epoxidised Oleum Cocois, rapeseed oil or soya-bean oil), defoamer, silicone oil for example, sanitas, viscosity modifier, tackiness agent, thickening material, and fertilizer or other activeconstituents.
When formula I activeconstituents was used for plant or its environment usually, amount of application was 0.001-4kg/ha, particularly 0.005-2kg/ha.Determine according to test for obtaining the desired result desired concn.According to the mode of action, the etap of crop and weeds, and use (place, time, method), can in very wide scope, change according to above-mentioned parameter concentration.
The weeding of formula I compound and the activity that suppresses growth are applicable in the useful crop it, cereal crop particularly, cotton, soybean, beet, sugarcane, raise crop, rape, corn and paddy rice, and the natural disposition control of weeds that is used to go out.Crop can also be understood that the crop that weedicide or a few class weedicide are had tolerance that those obtain by conventional breeding method or gene engineering, IMI corn for example, Poast Protected corn, Liberty Link corn, B.t./Liberty Link corn, IMI/Liberty Link corn, IMI/Liberty Link/B.t. corn, Roundup Ready corn and Roundup Ready/B.t. corn.Needing the weeds of control can be unifacial leaf or broadleaf weed, Stellaria for example, and the bean cotyledon Lepidium is cut gang Ying and is belonged to knotgrass, Avena, setaria, sinapsis alba belongs to, lolium, Solanum, Echinochloa, the Fischer grass belongs to, Monochoria, arrowhead belongs to, Brome, amur foxtail belongs to, Shi Mao, and Rottboellia exaltata L. F. belongs to, Cyperus, abutilon, chrysanthemum harvest spp, Xanthium, Amaranthus, Chenopodium, Ipomoea, crowndaisy chrysanthemum belongs to, Bedstraw, Viola and Veronica.
Advantageously formula I compound is mixed the preferred sulfonylurea of these weedicides, ureas with a large amount of other known weedicides, the chloro-acetophenone amine, chloroacetyl amine, diphenyl ether, the oil of mirbane amine, oxadiazole ketone, pyrazoles, triazines, (mixing) aryloxy propionic acid class, amino formate, thiocarbamates, thiophene triazines, cyclohexane diketone, imidazolone type, triazolopyrimidine sulfonamides, 2-pyrimidinyl oxy pyridine carboxylic acid and pyrimidine oxy-benzoic acid class.As a result, for example the remarkable grass extremely that enlarges of acquisition is composed the selectivity that has also also increased under many circumstances useful crop.As mentioned above, the blending ingredients of formula I compound also selectively exists with ester or salt form, for example is disclosed in The PesticideManual, and the 11st edition, 1997, BCPC.
Formula I compound and also can use with safener with the mixture of above-mentioned other weedicide.Preferred following suitable safener:
Formula S-I compound
Wherein
Rs
1Be hydrogen or chlorine, and
Rs
2Be hydrogen, C
1-C
8Alkyl or by C
1-C
6Alkoxyl group or C
3-C
6The C that alkenyloxy replaces
1-C
8Alkyl or formula S-II compound
E wherein
1Be nitrogen or methyne; Rs
3Be-CCl
3, phenyl or halogenophenyl; Rs
4And Rs
5Be hydrogen or halogen independently of one another; And Rs
6Be C
1-C
4Alkyl; Or formula S-III compound
Rs wherein
7And Rs
8Be hydrogen or halogen and Rs independently of one another
9, Rs
10And Rs
11Be C independently of one another
1-C
4Alkyl,
Or formula S-IV compound
Rs wherein
12It is group
Rs
13Be hydrogen, halogen, cyano group, trifluoromethyl, nitro, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl ,-COOH ,-COO-C
1-C
4Alkyl ,-CONRs
18Rs
19,-C (O)-C
1-C
4Alkyl, C (O)-phenyl, or by halogen, C
1-C
4The phenyl that alkyl, methoxyl group, nitro or trifluoromethyl replace, or-SO
2NRs
20Rs
21Or-OSO
2-C
1-C
4Alkyl;
Rs
18, Rs
19, Rs
20And Rs
21Be hydrogen or C independently of one another
1-C
4Alkyl, or Rs
18And Rs
19Or Rs
20And Rs
21Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted;
Rs
14Be hydrogen, halogen, C
1-C
4Alkyl, trifluoromethyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio ,-COOH or-COO-C
1-C
4Alkyl;
Or Rs
13And Rs
14Form C together
3-C
4Alkylidene bridge, this bridge can be by halogen or C
1-C
4Alkyl replaces, or Rs
13And Rs
14Form C together
3-C
4The alkylene group bridge, this bridge can be by halogen or C
1-C
4Alkyl replaces, or Rs
13And Rs
14Form C together
4Inferior alkadienyl bridge, this bridge can be by halogen or C
1-C
4Alkyl replaces;
Rs
15And Rs
16Be hydrogen independently of one another, C
1-C
8Alkyl, C
3-C
8Cycloalkyl, C
3-C
6Alkenyl, C
3-C
6Alkynyl,
, or by C
1-C
4Alkoxyl group or
The C that replaces
1-C
4Alkyl; Or Rs
15And Rs
16Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, sulphur, SO, SO
2, NH or-N (C
1-C
4Alkyl)-be interrupted;
Rs
22, Rs
23, Rs
24And Rs
25Be hydrogen independently of one another, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio ,-COORs
26, trifluoromethyl, nitro or cyano group, wherein Rs
26The hydrogen of respectively doing for oneself, C
1-C
10Alkyl, C
1-C
4Alkoxy-C
1-C
4Alkyl, C
1-C
4Alkylthio-C
1-C
4Alkyl, two-C
1-C
4Alkylamino-C
1-C
4Alkyl, halo-C
1-C
8Alkyl, C
2-C
8Alkenyl, halo-C
2-C
8Alkenyl, C
3-C
8Alkynyl, C
3-C
7Cycloalkyl, halo-C
3-C
7Cycloalkyl, C
1-C
8Alkyl-carbonyl, allyl group carbonyl, C
3-C
7Naphthene base carbonyl, unsubstituted benzoyl or on phenyl ring by halogen, C
1-C
4Alkyl, halo-C
1-C
4Alkyl, halo-C
1-C
4Alkoxyl group or C
1-C
4The benzoyl that alkoxyl group replaces for three times identical or differently at the most; Or furyl or thienyl; Or by phenyl, halogenophenyl, C
1-C
4Alkyl phenyl, C
1-C
4Alkoxyl phenyl, halo-C
1-C
4Alkyl phenyl, halo-C
1-C
4Alkoxyl phenyl, C
1-C
6Alkoxy carbonyl, C
1-C
4Alkoxy-C
1-C
8Alkoxy carbonyl, C
3-C
8Alkenyloxy carbonyl, C
3-C
8Alkynyloxy group carbonyl, C
1-C
8Alkylthio carbonyl, C
3-C
8Alkenyl thio carbonyl, C
3-C
8Alkynes sulfenyl carbonyl, formamyl, one-C
1-C
4Alkyl amino-carbonyl or two-C
1-C
4The C that alkyl amino-carbonyl replaces
1-C
4Alkyl; Or the phenyl amino carbonyl, this group itself can be by halogen, C on phenyl ring
1-C
4Alkyl, halo-C
1-C
4Alkyl, halo-C
1-C
4Alkoxyl group or C
1-C
4Alkoxyl group replaces or is replaced by cyano group or nitro one for three times identical or differently at the most; Or dioxolane-2-base, this group itself can be by one or two C
1-C
4Alkyl replaces, Huo diox-2-base, and this group itself can be by one or two C
1-C
4Alkyl replaces; Or by cyano group, nitro, carboxyl or C
1-C
8-alkylthio-C
1-C
8The C that alkoxy carbonyl replaces
1-C
4Alkyl;
Rs
17Be hydrogen or C
1-C
4Alkyl;
Rs
27Be hydrogen, halogen, nitro, C
1-C
4Alkyl or methoxyl group;
Rs
28Be hydrogen, halogen, C
1-C
4Alkyl, trifluoromethyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio ,-COOH or-COO-C
1-C
4Alkyl;
Rs
29Be hydrogen, halogen, cyano group, nitro, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl ,-COOH ,-COO-C
1-C
4Alkyl ,-CONRs
30Rs
31, C (O)-phenyl, or by halogen, C
1-C
4The phenyl that alkyl, methoxyl group, nitro or trifluoromethyl replace, or-SO
2NRs
32Rs
33,-OSO
2-C
1-C
4Alkyl, C
1-C
6Alkoxyl group, or by C
1-C
4The C that alkoxy or halogen replaces
1-C
6Alkoxyl group; Or C
3-C
6Alkenyloxy or the C that is replaced by halogen
3-C
6Alkenyloxy; Or C
3-C
6Alkynyloxy group; Rs wherein
30And Rs
31Be hydrogen or C independently of one another
1-C
4Alkyl; Or Rs
30And Rs
31Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted, and Rs
32And Rs
33Be hydrogen or C independently of one another
1-C
4Alkyl, or Rs
32And Rs
33Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted;
Rs
34Be hydrogen, halogen, nitro, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl ,-COOH ,-COO-C
1-C
4Alkyl or CONRs
35Rs
36, Rs wherein
35And Rs
36Be hydrogen or C independently of one another
1-C
4Alkyl, or Rs
35And Rs
36Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted;
Rs
37Be hydrogen, halogen, C
1-C
4Alkyl ,-COOH ,-COO-C
1-C
4Alkyl, trifluoromethyl or methoxyl group, or Rs
34And Rs
37Form C together
3-C
4Alkylidene bridge;
Rs
38Be hydrogen, halogen or C
1-C
4Alkyl;
Rs
39Be hydrogen, halogen, C
1-C
4Alkyl ,-COOH ,-COO-C
1-C
4Alkyl, trifluoromethyl or methoxyl group;
Rs
40Be hydrogen, halogen, nitro, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl ,-COOH ,-COO-C
1-C
4Alkyl or CONRs
42Rs
43
Rs
41Be hydrogen, halogen or C
1-C
4Alkyl; Or Rs
40And Rs
41Form C together
3-C
4Alkylidene bridge;
Rs
42And Rs
43Be hydrogen or C independently of one another
1-C
4Alkyl, or Rs
42And Rs
43Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted;
Rs
44Be hydrogen, halogen, C
1-C
4Alkyl ,-COOH ,-COO-C
1-C
4Alkyl, trifluoromethyl or methoxyl group;
Rs
45Be hydrogen, halogen, nitro, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl ,-COOH ,-COO-C
1-C
4Alkyl or CONRs
46Rs
47
Rs
46And Rs
47Be hydrogen or C independently of one another
1-C
4Alkyl, or Rs
46And Rs
47Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted;
Rs
48Be hydrogen, halogen, C
1-C
4Alkyl ,-COOH ,-COO-C
1-C
4Alkyl, trifluoromethyl or methoxyl group;
Rs
49Be hydrogen, halogen, nitro, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl ,-COOH ,-COO-C
1-C
4Alkyl or CONRs
50Rs
51
Rs
51And Rs
52Be hydrogen or C independently of one another
1-C
4Alkyl, or Rs
51And Rs
52Form C together
4-C
6Alkylidene bridge, this bridge can be by oxygen, NH or-N (C
1-C
4Alkyl)-be interrupted;
Or formula S-V compound
Rs wherein
53And Rs
54Be C independently of one another
1-C
6Alkyl or C
2-C
6Alkenyl; Or Rs
53And Rs
54Be together
Rs
55And Rs
56Be hydrogen or C independently of one another
1-C
6Alkyl;
Or Rs
53And Rs
54Be together
Rs wherein
55And Rs
56Be C independently of one another
1-C
4Alkyl, or Rs
55And Rs
56Be together-(CH
2)
5-;
Rs
57Be hydrogen, C
1-C
4Alkyl or
Or Rs
53And Rs
54Be together
Wherein
Rs
58, Rs
59, Rs
60, Rs
61, Rs
62, Rs
63, Rs
64, Rs
65, Rs
66, Rs
67, Rs
68, Rs
69, Rs
70, Rs
71, Rs
72And Rs
73Be hydrogen or C independently of one another
1-C
4Alkyl;
Or formula S-VI compound
Rs wherein
75Be hydrogen or chlorine and Rs
74Be cyano group or trifluoromethyl, or formula S-VII compound
Rs wherein
76Be hydrogen or methyl, or formula S-VIII compound
Wherein
R is 0 or 1;
Rs
77Be hydrogen or C
1-C
4Alkyl, wherein C
1-C
4Alkyl can be by C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl, C
1-C
4Halogenated alkoxy, C
1-C
4Halogenated alkylthio, C
1-C
4The haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl, nitro, cyano group ,-COOH, COO-C
1-C
4Alkyl ,-NRs
80Rs
81,-SO
2NRs
82Rs
83Or-CONRs
84Rs
85
Rs
78Be hydrogen, halogen, C
1-C
4Alkyl, trifluoromethyl, C
1-C
4Alkoxyl group or C
1-C
4Halogenated alkoxy;
Rs
79Be hydrogen, halogen or C
1-C
4Alkyl;
Rs
80Be hydrogen, C
1-C
4Alkyl or C
1-C
4Alkyl-carbonyl;
Rs
81Be hydrogen or C
1-C
4Alkyl; Or
Rs
80And Rs
81Form C together
4-or C
5-alkylidene group;
Rs
82, Rs
83, Rs
84And Rs
85Be hydrogen or C independently of one another
1-C
4Alkyl; Or Rs
82With Rs
83Together, or Rs
84And Rs
85Be C together independently of one another
4-or C
5-alkylidene group, wherein above-mentioned alkylidene group carbon atom can be replaced by oxygen or sulphur, or one or two carbon atom quilt-NH-or-N (C
1-C
4Alkyl)-replace;
E
2, E
3, E
4And E
5Be oxygen independently of one another, sulphur, C (Rs
86) Rs
87, carbonyl ,-NH-,-N (C
1-C
8Alkyl)-, group
Rs
86And Rs
87Be hydrogen or C independently of one another
1-C
8Alkyl; Or Rs
86And Rs
87Be C together
2-C
6Alkylidene group; Rs
88And Rs
89Be hydrogen or C independently of one another
1-C
8Alkyl; Or Rs
88And Rs
89Form C together
2-C
6Alkylidene group;
Rs
90Be Rs
91-O-, Rs
92-S-, or-NRs
93Rs
94
Rs
91And Rs
92Be hydrogen independently of one another, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
4Alkoxy-C
1-C
8Alkyl, C
3-C
6Alkenyloxy-C
1-C
8Alkyl or phenyl-C
1-C
8Alkyl, phenyl ring wherein can be by halogen, C
1-C
4Alkyl, trifluoromethyl, methoxyl group, methylthio group, methylsulfinyl or methyl sulphonyl replace, or C
3-C
6Alkenyl, C
3-C
6Halogenated alkenyl, phenyl-C
3-C
6Alkenyl, C
3-C
6Alkynyl, phenyl-C
3-C
6Alkynyl, trimethylene oxide (Oxetanyl), furyl or tetrahydrofuran base;
Rs
93Be hydrogen, C
1-C
8Alkyl, phenyl, phenyl-C
1-C
8Alkyl, phenyl ring wherein can by fluorine, chlorine, bromine, nitro, cyano group ,-OCH
3, C
1-C
4Alkyl or CH
3SO
2-replace, or C
1-C
4Alkoxy-C
1-C
8Alkyl, C
3-C
6Alkenyl or C
3-C
6Alkynyl;
Rs
94Be hydrogen, C
1-C
8Alkyl, C
3-C
6Alkenyl or C
3-C
6Alkynyl; Or
Rs
93And Rs
94Be C together
4-or C
5-alkylidene group, wherein above-mentioned alkylidene group carbon atom can be replaced by oxygen or sulphur, or one or two carbon atom quilt-NH-or-N (C
1-C
4Alkyl)-replace;
Rs
95And Rs
96Be hydrogen or C independently of one another
1-C
8Alkyl; Or
Rs
95And Rs
96Form C together
2-C
6Alkylidene group; And
Rs
97Be C
2-C
4Alkenyl or C
2-C
4Alkynyl; Condition is
A) annular atoms E
2, E
3, E
4And E
5In at least one is a carbonyl, and with this/a annular atoms that these annular atomses are adjacent is a group
Above-mentioned group only occurs once; And b) two adjacent annular atoms E
2And E
3, E
3And E
4, and E
4And E
5, can not be oxygen simultaneously; Or formula S-IX compound
Rs wherein
98Be hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
3-C
6Alkenyl or C
3-C
6Alkynyl; And Rs
99, Rs
100And Rs
101Be hydrogen independently of one another, C
1-C
6Alkyl, C
3-C
6Cycloalkyl or C
1-C
6Alkoxyl group, condition are Rs
99, Rs
100And Rs
101In a substituting group be not hydrogen;
Or formula S-X compound
E wherein
6Be nitrogen or methyne, work as E
6N is 0,1 when being nitrogen, 2 or 3 and work as E
6N is 0,1 when being methyne, 2,3 or 4, and Rs
102Be halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, nitro, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphonyl, C
1-C
4Alkoxy carbonyl, phenyl or phenoxy group, or separately by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, phenyl or phenoxy group that cyano group or nitro replace;
Rs
103Be hydrogen or C
1-C
4Alkyl;
Rs
104Be hydrogen, C
1-C
4Alkyl, C
3-C
6Cycloalkyl, C
2-C
6Alkenyl, C
2-C
6Alkynyl, C
1-C
4Haloalkyl, C
2-C
6Halogenated alkenyl, C
2-C
6The halo alkynyl, C
1-C
4Alkylthio-C
1-C
4Alkyl, C
1-C
4Alkyl sulphonyl-C
1-C
4Alkyl, C
1-C
4Alkoxy-C
1-C
4Alkyl, C
1-C
4Alkenyloxy-C
1-C
4Alkyl or C
1-C
4Alkynyloxy group-C
1-C
4Alkyl;
Or formula S-XI compound
E wherein
7Be oxygen or N-Rs
105And Rs
105It is the group of following formula
Rs wherein
106And Rs
107Be cyano group independently of one another, hydrogen, C
1-C
4Alkyl, C
3-C
6Cycloalkyl, C
2-C
6Alkenyl, aryl, phenyl or heteroaryl, or separately by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, the phenyl that cyano group or nitro replace, aryl or heteroaryl;
Or formula S-XII compound
E wherein
8Be oxygen, sulphur, sulfinyl, alkylsulfonyl or methyne,
Rs
108And Rs
109Be CH independently of one another
2COORs
112Or COORs
113Or represent Shi-(CH together
2) C (O)-O-C (O)-(CH
2)-group, and Rs
112And Rs
113Be hydrogen independently of one another, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
6Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, or metallic cation or ammonium cation; And
Rs
110And Rs
111Be hydrogen independently of one another, halogen or C
1-C
4Alkyl;
Or formula S-XIII compound
Rs wherein
114And Rs
115From being hydrogen independently, halogen or C
1-C
4Haloalkyl, Rs
116Be hydrogen, C
1-C
4Alkyl, C
3-C
4Alkenyl, C
3-C
4Alkynyl, C
1-C
4Haloalkyl, C
3-C
6Cycloalkyl, metallic cation or ammonium cation;
E
9Be nitrogen, methyne, C-F or C-Cl and
E
10It is the following formula group
, Rs wherein
118, Rs
119, Rs
121And Rs
122Be hydrogen or C independently of one another
1-C
4Alkyl;
Rs
117And Rs
120Be hydrogen independently of one another, C
1-C
4Alkyl, C
3-C
4Alkenyl, C
3-C
4Alkynyl, C
1-C
4Haloalkyl, C
3-C
6Cycloalkyl, metallic cation or ammonium cation;
Or formula S-XIV compound
Rs wherein
123Be hydrogen, cyano group, halogen, C
1-C
4Alkyl, C
3-C
6Cycloalkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkoxy carbonyl, C
1-C
4The alkylthio carbonyl ,-NH-Rs
125-C (O) NH-Rs
126, aryl or heteroaryl, or separately by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, aryl or heteroaryl that cyano group or nitro replace;
Rs
124Be hydrogen, cyano group, nitro, halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio; And
Rs
125And Rs
126Be C independently of one another
1-C
4Alkyl, C
1-C
4Haloalkyl, C
3-C
4Alkenyl, C
3-C
4Alkynyl, C
3-C
4Cycloalkyl, C
1-C
4Alkyl-carbonyl, C
1-C
4Alkyl sulphonyl, aryl or heteroaryl, or separately by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, aryl or heteroaryl that cyano group or nitro replace;
Or formula S-XV compound
Rs wherein
127And Rs
128Be hydrogen independently of one another, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, one-C
1-C
8-or two-C
1-C
8-alkylamino, C
3-C
6Cycloalkyl, C
1-C
4Alkylthio, phenyl or heteroaryl;
Rs
129Be hydrogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, one-C
1-C
8-or two-C
1-C
8-alkylamino, C
3-C
6Cycloalkyl, C
1-C
4Alkylthio, phenyl, heteroaryl, OH, NH
2, halogen, two-C
1-C
4-alkylamino, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphonyl or C
1-C
4Alkoxy carbonyl;
Rs
130Be hydrogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, one-C
1-C
8-or two-C
1-C
8-alkylamino, C
3-C
6Cycloalkyl, C
1-C
4Alkylthio, phenyl, heteroaryl, cyano group, nitro, carboxyl, C
1-C
4Alkoxy carbonyl, two-C
1-C
4-alkylamino, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphonyl, SO
2-OH, i-C
1-C
4Aminoalkyl group alkylsulfonyl or C
1-C
4The alkoxyl group alkylsulfonyl;
Rs
131Be hydrogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, one-C
1-C
8-or two-C
1-C
8-alkylamino, C
3-C
6Cycloalkyl, C
1-C
4Alkylthio, phenyl, heteroaryl, OH, NH
2, halogen, two-C
1-C
4-aminoalkyl group, tetramethyleneimine-1-base, piperidines-1-base, morpholine-1-base, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphonyl, C
1-C
4Alkoxy carbonyl, phenoxy group, naphthyloxy, phenyl amino, benzoyloxy or phenyl sulfonyloxy;
Or formula S-XVI compound
Rs wherein
132Be hydrogen, C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl or C
1-C
4Alkoxy-C
1-C
4Alkyl;
Rs
133Be hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl or C
1-C
4Alkoxyl group and Rs
134Be hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl or C
1-C
4Alkoxyl group; Condition is Rs
133And Rs
134Be not hydrogen simultaneously.
Particularly preferred safener is to be selected from following group compound in the present composition
Formula S1.1
And formula S1.2 compound
With formula SS1.3 compound
With formula S1.4 compound
With formula S1.5 compound
With formula S1.6 compound
With formula S1.7 compound
With formula S1.8 compound
With formula S1.9
Cl
2CHCON (CH
2CH=CH
2) (S1.9) and formula S1.10
With formula S1.11
With formula S1.12
Formula S1.1 to S1.13 compound is known and is disclosed in, The PesticideManual for example, the 11st edition, British Crop Protection Council, 1997, accession number is respectively 61 (formula S1.1, benoxacors), 304 (formula S1.2, fenclorim), 154 (formula S1.3, cloquintocets), 462 (formula S1.4, pyrroles's two diethyl phthalates), 377 (formula S1.5, furilazole), 363 (formula S1.8, fluxofenims), 213 (formula S1.9, dichlormides) and 350 (formula S1.10 separates careless amine).Formula S1.11 compound is known, and general MON4660 by name (Meng Shandou) also is disclosed in, and for example EP-A-0 436 483.
Formula S1.6 compound (AC 304415) is disclosed in, and for example EP-A-0 613 618, and formula S1.7 compound is disclosed among the DE-A-2948535.Formula S1.12 compound is disclosed among the DE-A-4331448, and formula S1.13 compound is disclosed among the DE-A-3525205.
The following example is used for further explaining the present invention but is not restricted to this.
Preparation embodiment:
Embodiment P1: preparation 3-hydroxyl-4-aryl-5-oxo-pyrazoline
With vinylidene chloride (84ml, 1.05M), nitrite tert-butyl (12.5ml, 0.105M) and cupric chloride (II) put into acetonitrile (70ml).Under 10 ℃, add 2,6-two bromo-4-N-methyl-p-nitroanilines 1 to wherein merotomizing.Then reaction mixture was also filtered in stirring at room in 16 hours, and use the t-butyl methyl ether wash filtrate.With organic phase 150ml 10%HCl and 2 * 150ml water washing, and use Na
2SO
4Dry.Organic phase is concentrated and uses the silica gel chromatography purifying.Obtain 13.2g compound 2.
1H-NMR(300MHz，CDCl
3)：δ＝4.69(s，2H)。
(10.9g 26.4mmol) is suspended in the methyl alcohol and at room temperature adds NaOMe solution (in 30% methyl alcohol, 27.8ml) with compound 2.With reaction mixture refluxed 1 hour, H was used in cooling then
2SO
4(3.7ml) making it acidifying also refluxed 0.5 hour again.With the reaction mixture cooling, dilute with water is also used CH
2Cl
2(3 * 100ml) extractions.With the organic phase Na that merges
2SO
4Drying is filtered and is concentrated.Obtain the compound 3 (9.1g) of crude product form.
1H-NMR(300MHz，CDCl
3)：δ＝8.4(s，2H)；4.2(s，2H)；3.7(s，3H)。
(9.1,25.7mmol) (18ml 61.7mmol) adds in the toluene with the vinyl tributyl tin with compound 3.Reaction mixture is fed argon to outgas 0.33 hour.Then to wherein add four (triphenylphosphine)-Pd (O) (1.46g, 1.28mmol).Reaction mixture was also cooled off 100 ℃ of heating in 16 hours, and adding NaOH solution (1N, 100ml).High-speed stirring two-phase mixture 0.5 hour.Separate organic phase and water and salt water washing, Na
2SO
4Drying concentrates and silica gel chromatography (EtOAc: purifying hexane (1: 10)).Obtain compound 4 (4.13g).
1H-NMR(300MHz，CDCl
3)：δ＝8.2(s，2H)；6.9(dd，1H)；5.8(d，1H)；5.5(d，1H)；3.8(s，2H)；3.7(s，3H)。
With compound 4 (4g 16.2mmol) is dissolved among the MeOH (100ml), to wherein add Pd/C (5%, 2g).The high-speed stirring reaction mixture is 2.5 hours under atmosphere of hydrogen (normal pressure).Reaction mixture is filtered and concentrates.Obtain compound 5 (3.25g).
1H-NMR(300MHz，CDCl
3)：δ＝6.4(s，2H)；3.7(s，3H)；3.6(s，2H)；2.6(q，4H)；1.2(t，6H)
With nitrite tert-butyl (5.96ml, 50mmol) and methylene iodide (4.15ml 50mmol) adds in the acetonitrile (30ml), and under 0 ℃, to wherein add the compound 5 that has been dissolved in acetonitrile (20ml) (5.52g, 25mmol).With 1 hour (200W) of reaction mixture illumination, temperature rises to 70 ℃ in this process.With the reaction mixture cooling, add entry, and extract (2 * 20ml) with ethyl acetate.With organic phase 1N HCl and the salt water washing that merges, Na
2SO
4Drying is filtered, and concentrates and by silica gel chromatography (ethyl acetate: hexane=1: 5).Obtain compound 6 (Hal=I) (1.6g).
1H-NMR(300MHz，CDCl
3)：δ＝7.4(s，2H)；3.7(2S，5H)；2.6(q，4H)；1.2(t，6H)。
With Diisopropylamine (565mg 5.59mmol) adds among the THF (15ml), and-30 ℃ add down n-BuLi (2M, the cyclohexane solution of n-BuLi, 2.67ml, 5.34mmol).Reaction mixture was descended stirring 0.25 hour and was cooled to-78 ℃ at 0 ℃.Compound 6 (Hal=I) is dissolved among the THF (15ml) and dropwise is added in the reaction mixture.After stirring 0.5 hour under-78 ℃, add cyano methyl formate, and reaction mixture slowly is heated to 0 ℃.Reaction mixture is added NH
4Cl (aqueous solution) (100ml) in and with ethyl acetate (2 * 70ml) extraction.With the organic phase H that merges
2O (3 * 70ml) and salt solution (70ml) washing, Na
2SO
4Drying is filtered and is concentrated.Crude product is passed through the silica gel chromatography purifying.
Acquisition compound 7 (Hal=I, 1.125g).
1H-NMR(300MHz，CDCl
3)：δ＝7.4(s，2H)；5.0(s，1H)；3.8(s，6H)；2.6(m，4H)；1.2(m，6H)。
With nitrite tert-butyl (355ml, 3mol) and cupric chloride (II) (337.4g 2.5mol) adds in the acetonitrile (1200ml).At first, under＜30 ℃, (2385ml 29.9mol), under 10 ℃, dropwise adds 4-bromo-2 then, 6-xylidine 8 (398g, acetonitrile 2mol) (2000ml) solution dropwise to add vinylidene chloride.Then reaction mixture was at room temperature stirred 16 hours, stir and be added to 20%HCl (9000ml) also with t-butyl methyl ether (3 * 3000ml) extractions.With organic phase with 20%HCl and water washing and use Na
2SO
4Dry.Concentrate organic phase.Obtain 470g compound 9.
1H-NMR(300MHz，CDCl
3)：δ＝4.13(s，2H)。
With compound 9 (257g 0.813mol) is dissolved in the methyl alcohol (400ml), and under＜30 ℃, add NaOMe (30% methanol solution, 640ml, 3.53mol).Reaction mixture refluxed was stirred 15 hours.Reaction mixture is cooled to room temperature, and the adding vitriol oil (95ml, 1.75mol).Reaction mixture refluxed was stirred 10 hours, concentrate and blunge.Suspension is extracted and uses Na with methylene dichloride (3x)
2SO
4The dry organic phase that merges concentrates and distillation.
Obtain compound 10 (198g, b.p.:95-100 ℃/0.2).
1H-NMR(300MHz，CDCl
3)：δ＝3.67(s，3H)；3.62(s，2H)；2.28(s，6H)。
With sodium hydride (60g, 1.6mol) be suspended in methylcarbonate (1500ml, 17.7mol) in and be heated to 90 ℃.(1200ml, (198g 0.77mol) dropwise is added in the reaction mixture compound 10 14.2M) will to be dissolved in methylcarbonate.Reaction mixture was stirred 20 hours down and cooling at 90 ℃, remove excessive sodium hydride with methyl alcohol then.Reaction mixture is poured in ice/water, regulated pH=5, use methylene dichloride (4x) extraction then with HCl.With the organic phase salt water washing that merges, Na
2SO
4Drying concentrates and with ethyl acetate/hexane (1: 10) recrystallization.Obtain compound 11 (161.33g, m.p.:69-71 ℃).
1H-NMR(300MHz，CDCl
3)：δ＝7.21(s，2H)；4.98(s，1H)；3.76(s，6H)，2.31(s，6H)。
With compound 11 (40g, 0.129mol) and hydrazine 16 (27.15,0.155mol) be suspended in the dimethylbenzene (500ml) and in reaction mixture, feed the argon degassing 0.3 hour.(43ml 0.1552mol), stirs them 4 hours down at 140 ℃ to add triethylamine in reaction mixture.Reaction mixture is cooled to room temperature and concentrated, stirs resistates and use ethyl acetate extraction 3 times with 10%HCl then.With the organic phase salt water washing that merges, Na
2SO
4Dry and concentrated.Obtain compound 17 (42.87g, m.p.:299-301 ℃).
1H-NMR (300MHz, CDCl
3): δ=7.26 and 7.18 (2s, 2H); 4.70 (s, 1H); 4.20-3.75 (m, 8H); 2.41 (s, and 3H) 2.08 (s, 3H).
With compound 17 (42.87g 0.12mol) is suspended in the acetonitrile (400ml), add then triethylamine (29ml, 0.206mol).This etching solution is clarifying, and this solution is cooled to 10 ℃, and adding diethylacbamazine acyl chloride (26.2ml, 0.206mol).With reaction mixture refluxed heating 10 hours, be cooled to room temperature, regulate pH=5 in the impouring ice/water and with dense HCl.With reaction mixture several times with ethyl acetate extraction.With the organic phase salt water washing that merges, Na
2SO
4Dry and concentrated.The gained resinous substance is stirred with ether.The crystallization 18 (47g, m.p.122 ℃) that obtains is leached.
1H-NMR(300MHz，CDCl
3)：δ＝7.21(s，2H)；4.28(m，2H)；3.92(m，6H)；3.2(m，4H)；2.22(s，6H)，1.0(m，6H)。
With 18 (2.76g, 6.1mmol), yellow soda ash (the 2M aqueous solution of 2.5ml, 9.98mmol) and phenyl-boron dihydroxide (0.18g 8.88mmol) is suspended in 1, feeds the argon degassing in the 2-diethoxyethane and in reaction mixture.Add tetrakis triphenylphosphine palladium (0.36g, 0.312mmol) after, reaction mixture refluxed was stirred 8 hours, cooling is in the impouring water and be adjusted to pH=5 with dense HCl.With ethyl acetate extraction 3 times, will merge organic phase salt water washing, Na
2SO
4Drying concentrates and by silica gel chromatography (ethyl acetate: methyl alcohol=5: 1).Obtain compound 19 (2.7g).
1H-NMR(300MHz，CDCl
3)：δ＝7.7-7.25(m，7H)；4.3(m，2H)；3.92(m，6H)；3.2(m，4H)；2.29(s，6H)，0.95(m，6H)。
With compound 19 (4.0g 8.9mmol) is dissolved in the methyl alcohol (50ml), add sodium hydroxide solution (2N, 17.6ml, 17.8mmol).Reaction mixture refluxed was stirred 12 hours, and cooling also concentrates.Resistates and water are stirred and is adjusted to pH with dense HCl is 3.Sedimentable matter is leached and drying.Obtain compound 20 (3.1g, m.p.:260-261 ℃).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.25(m，7H)；4.26(m，2H)；4.0(m，4H)；3.85(m，2H)；2.50(s，3H)，2.16(s，3H)。
With compound 20 (1.04g 2.96mmol) puts into acetonitrile (25ml), add triethylamine (0.49ml, 3.55mmol) and the PIVALIC ACID CRUDE (25) muriate (0.45ml, 3.55mmol).Reaction mixture was at room temperature stirred 1 hour, concentrate, stirring and be adjusted to pH with dense HCl with water is 0.5.With ethyl acetate extraction 3 times, with the organic phase salt water washing that merges, Na
2SO
4Drying concentrates and by silica gel chromatography (ethyl acetate: methyl alcohol=5: 1).Obtain compound 21 (0.93g, m.p.159 ℃).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.25(m，7H)；4.3(m，2H)；3.94(m，2H)；3.85(m，4H)；2.28(s，6H)，1.05(s，9H)。
With 4-phenylbenzene carbonyl chloride 12 (25g 0.115mol) is dissolved in the acetonitrile (150ml), is cooled to 0 ℃, and add diethylamine (18.6g, 0.254mol).Reaction mixture was at room temperature stirred 0.5 hour, concentrate, be dissolved in the ethyl acetate (200ml) and water (2 * 100ml) and NaHCO
3The aqueous solution (100ml) washing, Na
2SO
4Dry and concentrated.From Et
2Crystallization goes out crude product (28.5g) in the O/ hexane.Obtain compound 13 (24.5g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.35(m，9H)；3.7-3.2(2bs，4H)；1.2(m，6H)。
With TMEDA (17.1g, 0.147mol) be dissolved in THF (Na is distilled, 500ml) in, be cooled to-78 ℃, and add s-BuLi (the 1.3M cyclohexane solution of 113ml, 0.147mol).Reaction mixture was stirred 0.25 hour down at-78 ℃, and (33.9g, THF 0.134mol) (100ml) solution was with mixture-78 ℃ following restir 0.25 hour to wherein dropwise adding 13.(45.2g 0.29mol) dropwise handles and is heated to 0 ℃ with iodoethane with reaction mixture.In reaction mixture, add saturated NH
4The Cl aqueous solution (200ml).Leach organic phase, use the salt water washing, Na
2SO
4Drying concentrates and by silica gel chromatography (Et
2O/ hexane=1: 1).Obtain compound 22 (29.5g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.2(m，9H)；3.9-3.1(m，4H)；2.7(q，2H)，1.25(t，6H)；1.1(t，3H)。
With Diisopropylamine (13.36g, 0.132mol) be dissolved in THF (Na is distilled, 400ml) in, be cooled to-30 ℃ and add n-BuLi (the 1.6M hexane solution of 79ml, 0.126mol).0.25 after hour, reaction mixture is cooled to-78 ℃, slowly add TMEDA (15.3g, 0.132mol) and be dissolved in THF (75ml) 22 (29.5g, 0.105mol).0.3 after hour, in reaction mixture, add the chlorine trimethyl silyl, be heated to 0 ℃.In reaction mixture, add saturated NH
4The Cl aqueous solution (200ml), separately organic phase.With salt water washing organic phase, Na
2SO
4Dry and concentrated.Obtain the compound 23 (38.2) of crude product form.
1H-NMR (300MHz, CDCl
3): δ=7.6-7.1 (m, 8H); 3.75 (m, 1H); 3.4-3.0 (m, 3H); 2.3 and 2.1 (2m, 1H); 1.35 (d, 3H); 1.25 (m, 6H); 0.0 (s, 9H).
With TMEDA (8.9g, 0.077mol) be dissolved in THF (Na is distilled, 400ml) in, reaction mixture is cooled to-78 ℃, dropwise add s-BuLi (cyclohexane solution of 59ml 1.3M, 0.077mol), dropwise add 23 (24.8g, THF 0.07mol) (75ml) solution then.-78 ℃ after following 0.5 hour, (13.3g 0.085mol), is heated to 0 ℃ to add methyl iodide in reaction mixture.In reaction mixture, add saturated NH
4The Cl aqueous solution (200ml) leaches organic phase.With salt water washing organic phase, Na
2SO
4Dry and concentrated.Crude product is passed through silica gel chromatography (ethyl acetate/hexane=1: 7).Obtain compound 24 (18.5).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.2(m，7H)；3.6(m，2H)；3.1(m，2H)；2.6(m，2H)；2.1(m，1H)；1.4(d，3H)；1.2(m，6H)；0.0(s，9H)。
With 24 (18.5g 0.059mol) is dissolved in DMF (100ml) and the water (10ml), room temperature add CsF (11.2g, 0.074mol).Reaction mixture was stirred 8 hours down at 75 ℃, and (2 * 100ml) extract in the impouring water (300ml) and with ethyl acetate.With the organic phase salt water washing that merges, Na
2SO
4Dry and concentrated.Obtain the compound 25 (15.7g) of crude product form.
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.3(m，7H)；3.6(m，2H)；3.15(m，2H)；2.6(m，2H)；1.3(m，9H)；1.05(t，3H)。
(15.7g 0.051mol) is dissolved in the toluene, adds LiAlH with 25
4(1.92g, 0.051mol).Reaction mixture refluxed stirred 20 hours and be cooled to 0 ℃, add carefully HCl solution (1N, 150ml), ethyl acetate (2 * 100ml) extractions.With (1 * 75ml) extraction of the organic phase that merges 1N HCl solution.It is 11 that the water that merges is adjusted to pH with 2N NaOH solution, with ethyl acetate (2 * 100ml) extractions.With the organic phase Na that merges
2SO
4Dry and concentrated.Obtain the compound 26 (8.6g) of crude product form.
1H-NMR(300MHz，CDCl
3)：δ＝7.8-7.25(m，7H)；3.6(s，2H)；3.35(q，4H)；2.5(q，4H)；1.25(t，6H)；1.05(t，6H)。
With 26 (8.6g 0.029mol) is dissolved in the toluene (50ml), add Vinyl chloroformate (12.6g, 0.116mol).Reaction mixture was stirred 3 hours down at 75 ℃, and concentrate.Obtain the crude product (11g) of compound 27.
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.3(m，7H)；4.75(s，2H)；2.9(q，4H)；1.3(t，6H)。
(the 11g crude product, 0.029mol) (2.87g 0.044mol) refluxes together and stirred 20 hours with the potassium cyanide of fine grinding in acetonitrile (100ml) with 27.Add again potassium cyanide (2.87g, 0.044mol) after, reaction mixture refluxed again stirred 24 hours, cooling is in the impouring water (300ml) and with ethyl acetate (2 * 100ml) extractions.With the organic phase salt water washing that merges, Na
2SO
4Drying, and concentrate.Obtain the crude product (10g) of compound 28.
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.3(m，7H)；3.7(s，2H)；2.8(q，4H)；1.4(t，6H)。
(4.5g 0.018mol) refluxes in acetate (25ml) and HCl (37% aqueous solution) and stirred 24 hours with 28.Acetate is distilled, and water (100ml) diluted reaction mixture is also used methylene dichloride (2 * 100ml) extractions.With the organic phase Na that merges
2SO
4Dry and concentrated.Obtain compound 29 crude products (5g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.3(m，7H)；3.8(s，2H)；2.7(q，4H)；1.25(t，6H)。
(8.1g 0.03mol) is dissolved in the toluene (75ml), adds SOCl with 29
2(8.9g, 0.075mol).Reaction mixture is heated to reflux temperature and after stopping to emit gas, concentrates.The oil of gained is dissolved in the toluene (50ml), adds MeOH (20ml), and mixture was at room temperature stirred 0.5 hour and concentrated.Obtain compound 30 crude products (9.1g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.3(m，7H)；3.8(s，2H)；3.7(s，3H)；2.7(q，4H)；1.25(t，6H)。
With 30 (9.1g, 0.032mol) be dissolved in the methylcarbonate (75ml) and with solution add sodium hydride suspension (3.24g 60% mineral oil dispersion, 0.081mol) in.Reaction mixture refluxed was stirred 20 hours, be cooled to room temperature, and slowly add 1N HCl solution (100ml).After stopping to emit gas, with reaction mixture with ethyl acetate (2 * 100ml) extractions, and with the organic phase salt water washing that merges, Na
2SO
4Dry and concentrated.Obtain compound 31 crude products (11.3g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.2(m，7H)；5.1(s，1H)；3.7(s，6H)；2.7(q，4H)；1.2(t，6H)。
With TMEDA (15.1g 0.13mol) is dissolved among the THF (500ml) and is cooled to-78 ℃, dropwise add s-BuLi (the 1.3M cyclohexane solution of 100ml, 0.13mol).(30g 0.12mol) is dissolved among the THF (100ml), and solution was dropwise added in the reaction mixture in 0.5 hour with 13.At-78 ℃ after following 0.5 hour, in reaction mixture, add trimethyl borate again.Reaction mixture was stirred 0.5 hour down at-78 ℃, be heated to-40 ℃, to wherein adding NH
4The Cl aqueous solution (250ml).With organic phase salt water washing, Na
2SO
4Dry and concentrated.Obtain compound 32 crude products (36.7g).
(35.2g 0.12mol) adds among the MeOH (300ml), and add H under ice-cooled condition with 32
2O
2(30% solution of 16.1g 0.142mol), rises to 40 ℃ with temperature of reaction from 20 ℃.After 2 hours, reaction mixture is concentrated into 2/3, adds crystal seed and water (500ml).The gained crystallization is leached and washes with water.Obtain compound 33 (30g).
1H-NMR(300MHz，CDCl
3)：δ＝7.65-7.2(m，7H)；7.05(dd，1H)；3.05(q，4H)；1.3(t，6H)。
With 33 (3.7g 13.7mmol) adds among the DMF, and add NaH (60% dispersion of 0.55g, 13.7mmol).After waiting to stop releasing hydrogen gas, (2.0g 16mmol), at room temperature stirred it 1 hour, and (2 * 100ml) extract among the HCl (300ml) of impouring dilution and with ethyl acetate then to add methyl-sulfate in reaction mixture.With the organic phase salt water washing that merges, Na
2SO
4Drying concentrates and by silica gel chromatography (ethyl acetate: hexane, 1: 1).Obtain compound 34 (3.4g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.2(m，8H)；3.9(s，3H)；3.6(bm，2H)；3.2(q，2H)；1.3(t，3H)；1.1(t，3H)。
(1.49g 12.8mmol) is dissolved among the THF (50ml) and is cooled to-78 ℃ with TMEDA.In reaction mixture, add s-BuLi (the 1.3M cyclohexane solution of 9.8ml, 12.8mmol), it was stirred 0.25 hour down at-78 ℃, and (3.3g, (15ml) solution of THF 11.6mmol) also stirs mixture 0.3 hour under-78 ℃ dropwise to add compound 34.In reaction mixture, add iodoethane (2.0g, 13mmol).Reaction mixture is heated to 0 ℃ and add NH
4The Cl aqueous solution (50ml).With organic phase salt water washing, Na
2SO
4Dry and concentrated.Obtain compound 35 crude products (3.5g).
1H-NMR(300MHz，CDCl
3)：δ＝7.6-7.3(m，5H)；7.07(s，1H)；6.9(s，1H)；3.9(s，3H)；3.8(m，1H)；3.45(m，1H)3.2(m，2H)；2.6(m，2H)；1.3(m，6H)；1.1(t，3H)。
Under the room temperature with N, N '-diacetyl hydrazine 14 (768g, 6.62mol), 2,2 '-dichloro-diethyl ether (1141g, 7.9mol) and salt of wormwood (1827g 13.3mol) adds among the DMF (8.5 liters).130 ℃ of heating 3.5 hours, cooling was filtered and is concentrated with gained suspension.Resistates is dissolved in the toluene (1000ml) and stirred 16 hours at 0 ℃.After the filtration, obtain white crystals shape product 15 (574g).Mother liquor is passed through evaporation concentration and recrystallization from small amount of methanol.Obtain the product 15 (108g) of white crystals shape once more.
Under 35 ℃ with 15 (1000g 5.38mol) is dissolved in the anhydrous methanol (5.4 liters), and dropwise add Acetyl Chloride 98Min. (1688g, 21.5mol).After dripping end, reaction mixture was stirred 16 hours at 55 ℃.With reaction mixture cooling and be concentrated into about 1.4 liters, stir down at 0 ℃-10 ℃ then.The crystallization that forms in the said process is leached and wash with ether (1.5 liters).Obtain the product 16 (520g) of white crystals shape.
1H-NMR(300MHz，D
6-DMSO)：δ＝3.8(s，4H)；3.4(s，4H)。
Obtained listed compound in the following table with similar approach.
In the table below, " LC/MS:M
+" represent to analyze the molecular weight of determining according to coupling HPLC (high performance liquid chromatography) and MS (mass spectroscopy); The UV spectrographic maximum absorption frequency of representing with nanometer that the numeral that provides after " UV " is measured in water/acetonitrile.Table 1 following formula: compound
Ph=phenyl table 2 following formula: compound
Ph=phenyl table 3 following formula: compound
Ph=phenyl table 4 following formula: compound
The Ph=phenyl
| The compound sequence number | R 1 | R 2 | ?R 3 | ?G | Physicochemical constant |
| Ia-1 | ?CH 3 | ?Ph | ?CH 3 | ?H | ?m.p.260-261℃ |
| Ia-2 | ?CH 3 | ?Ph | ?CH 3 | ?C(O)C(CH 3) 3 | ?m.p.159-161℃ |
| Ia-3 | ?CH 3 | ?Ph | ?CH 3 | ?C(O)N- (CH 2CH 3) 2 | Resinous substance |
| Ia-4 | ?CH 2CH 3 | ?Ph | ?CH 2CH 3 | ?H | ?m.p.＞250℃ |
| Ia-5 | ?CH 2CH 3 | ?Ph | ?CH 2CH 3 | ?C(O)C(CH 3) 3 | ?m.p.162-164℃ |
| Ia-6 | ?CH 2CH 3 | ?Ph | ?OCH 3 | ?H | ?m.p.205-207℃ |
| Ia-7 | ?CH 2CH 3 | ?Ph | ?OCH 3 | ?C(O)C(CH 3) 3 | ?m.p.57-59℃ |
| Ia-8 | ?CH 2CH 3 | ?Ph | ?SCH 3 | ?H | ?m.p.200-201℃ |
| Ia-9 | ?CH 2CH 3 | ?Ph | ?SCH 3 | ?C(O)C(CH 3) 3 | ?m.p.197-199℃ |
| Ia-10 | ?CH 2CH 3 | ?Ph | ?S(O) 2CH 3 | ?C(O)C(CH 3) 3 | ?m.p.172-174℃ |
| Ia-11 | ?CH 2CH 3 | ?Ph | ?CH 2Ph | ?H | ?m.p.203-205℃ |
| Ia-12 | ?CH 3 | ?4-CH 2＝CH-Ph | ?CH 3 | ?H | (LC/MS： ?M +＝376) |
| Ia-13 | ?CH 3 | ?2-Cl-Ph | ?CH 3 | ?H | (LC/MS： ?M +＝384) |
| Ia-14 | ?CH 3 | ?4-Cl-Ph | ?CH 3 | ?H | (LC/MS： M +＝384) |
| Ia-15 | ?CH 3CH 2 | ?4-Cl-Ph | ?CH 3CH 2 | ?H | (LC/MS： M +＝412) |
| Ia-16 | ?CH 3 | ?3-Br-Ph | ?CH 3 | ?H |
| The compound sequence number | ?R 1 | R 2 | ?R 3 | ?G | Physicochemical constant |
| Ib-1 | ?CH 3 | ?Ph | ?CH 3 | ?H | ?m.p.239-240℃ |
| Ib-2 | ?CH 3 | ?Ph | ?CH 3 | ?C(O)C(CH 3) 3 | Resinous substance |
| Ib-3 | ?CH 3 | ?Ph | ?CH 3 | ?C(O)N-(CH 2CH 3) 2 | Resinous substance |
| Ib-4 | ?CH 3 | ?Ph | ?CH 3 | ?C(O)O-CH 2CH 3 | ?m.p.144-146℃ |
| Ib-5 | ?CH 3 | ?Ph | ?CH 3 | ?C(O)CH 3 | ?m.p.198-199℃ |
| Ib-6 | ?CH 3 | ?Ph | ?CH 3 | C (O) cyclopropyl | ?m.p.104-105 |
| Ib-7 | ?H | ?Ph | ?CH 2CH 3 | ?H | ?m.p.176-177℃ |
| Ib-8 | ?H | ?Ph | ?CH 2CH 3 | ?C(O)C(CH 3) 3 | ?m.p.128-130℃ |
| Ib-9 | ?CH 2CH 3 | ?Ph | ?CH 2CH 3 | ?H | ?m.p.＞250℃ |
| Ib-10 | ?CH 2CH 3 | ?Ph | ?CH 2CH 3 | ?C(O)C(CH 3) 3 | ?m.p.166-168℃ |
| Ib-11 | ?CH 2CH 3 | ?Ph | ?SCH 3 | ?H | ?m.p.170-172℃ |
| Ib-12 | ?CH 2CH 3 | ?Ph | ?SCH 3 | ?C(O)C(CH 3) 3 | ?m.p.182-183℃ |
| Ib-13 | ?CH 2CH 3 | ?Ph | ?OCH 3 | ?H | ?m.p.148-150℃ |
| Ib-14 | ?CH 2CH 3 | ?Ph | ?OCH 3 | ?C(O)C(CH 3) 3 | ?m.p.127-129℃ |
| Ib-15 | ?CH 2CH 3 | ?Ph | ?C≡CSi(CH 3) 3 | ?H | ?m.p.150-152℃ |
| Ib-16 | ?CH 2CH 3 | ?Ph | ?C≡CSi(CH 3) 3 | ?C(O)C(CH 3) 3 | ?m.p.69-71℃ |
| Ib-17 | ?CH 2CH 3 | ?Ph | ?C≡CSi(CH 3) 3 | ?C(O)N-(CH 2CH 3) 2 | ?m.p.134-136℃ |
| Ib-18 | ?CH 2CH 3 | ?Ph | ?C≡CH | ?H | ?m.p.108-111℃ |
| Ib-19 | ?CH 2CH 3 | ?Ph | ?C≡CH | ?C(O)C(CH 3) 3 | ?m.p.134-136℃ |
| Ib-20 | ?CH 2CH 3 | ?Ph | ?Br | ?H | ?m.p.221-222℃ |
| Ib-21 | ?CH 2CH 3 | ?Ph | ?Br | ?C(O)C(CH 3) 3 | ?m.p.153-154℃ |
| Ib-22 | ?CH 2CH 3 | ?Ph | ?Br | ?C(O)N-(CH 2CH 3) 2 | ?m.p.129-131℃ |
| Ib-23 | ?CH 2CH 3 | ?Ph | ?CH 2Ph | ?H | ?m.p.247-249℃ |
| Ib-24 | ?CH 2CH 3 | ?Ph | ?CH 2Ph | ?C(O)C(CH 3) 3 | Resinous substance |
| Ib-25 | ?CH 3 | ?3-CF 3-Ph | ?CH 3 | ?H | ?m.p.225-226℃ |
| Ib-26 | ?CH 3 | ?3-CF 3-Ph | ?CH 3 | ?C(O)C(CH 3) 3 | ?m.p.197-199℃ |
| Ib-27 | ?CH 3 | ?3-CF 3-Ph | ?CH 3 | ?C(O)N-(CH 2CH 3) 2 | Oily matter |
| Ib-28 | ?CH 3 | ?3-CF 3-Ph | ?CH 3 | ?C(O)O-CH 2CH 3 | Resinous substance |
| Ib-29 | ?CH 3 | ?4-F-Ph | ?CH 3 | ?H | |
| Ib-30 | ?CH 3 | ?4-F-Ph | ?CH 3 | ?C(O)C(CH 3) 3 | |
| Ib-31 | ?CH 3 | ?4-F-Ph | ?CH 3 | ?C(O)N-(CH 2CH 3) 2 | Oily matter |
| Ib-32 | ?CH 3 | ?4-CF 3-Ph | ?CH 3 | ?H | ?m.p.294-296℃ |
| Ib-33 | ?CH 3 | ?4-CF 3-Ph | ?CH 3 | ?C(O)C(CH 3) 3 | ?m.p.160-161℃ |
| Ib-34 | ?CH 3 | ?4-CF 3-Ph | ?CH 3 | ?C(O)N-(CH 2CH 3) 2 | ?m.p.68-70℃ |
| Ib-35 | ?CH 3 | ?4-CF 3-Ph | ?CH 3 | ?C(O)OCH 2CH 3 | Resinous substance |
| Ib-36 | ?CH 3 | ?3-NO 2-Ph | ?CH 3 | ?H | ?m.p.219-221℃ |
| Ib-37 | ?CH 3 | ?3-NO 2-Ph | ?CH 3 | ?C(O)C(CH 3) 3 | ?m.p.180-182℃ |
| Ib-38 | ?CH 3 | ?3-NO 2-Ph | ?CH 3 | ?C(O)N-(CH 2CH 3) 2 | |
| Ib-39 | ?CH 3 | ?4-CH 2＝CH-Ph | ?CH 3 | ?H | (LC/MS： M +＝360) |
| Ib-40 | ?CH 3 | ?2-Cl-Ph | ?CH 3 | ?H | (LC/MS： M +＝368) |
| Id-41 | ?CH 3 | ?4-Cl-Ph | ?CH 3 | ?H | (LC/MS： M +＝368) |
| Ib-42 | ?CH 2CH 3 | ?4-Cl-Ph | ?CH 2CH 3 | ?H | (LC/MS： ?M +＝396) |
| Ib-43 | ?CH 3 | ?3-Br-Ph | ?CH 3 | ?H | (LC/MS： M +＝412) |
| Ib-44 | ?CH 3 | ?2-CH 3O-Ph | ?CH 3 | ?H | (LC/MS： M +＝364) |
| Ib-45 | ?CH 3 | ?4-CH 3O-Ph | ?CH 3 | ?H | (LC/MS： M +＝364) |
| The compound sequence number | ?R 1 | R 2 | ?R 3 | ?R 4 | ?R 5 | ?G | Physicochemical constant |
| Ic-1 | ?CH 3 | ?Ph | ?CH 3 | ?CH 3 | ?CH 3 | ?C(O)N- (CH 2CH 3) 2 | Resinous substance |
| Ic-2 | ?CH 2CH 3 | ?Ph | ?OCH 3 | ?H | (CH 2) 3OH | ?H | ?m.p.91-93℃ |
| Ic-3 | ?CH 3 | ?Ph | ?CH 3 | ?CH 3 | ?CH 3 | ?H | ?m.p.197℃ |
| The compound sequence number | ??R 1 | R 3 | Physicochemical constant |
| ??Id-1 | ??CH 3 | ??CH 3 | ??m.p.?68- ??69℃ |
| ??Id-2 | ??CH 2CH 3 | ??SCH 3 | Oily matter |
| Id-3 | ??CH 2CH 3 | ??OCH 3 | Oily matter |
| Id-4 | ??CH 2CH 3 | ?CH 2CH 3 | Oily matter |
| Id-5 | ??CH 2CH 3 | ?CH 2Ph | Oily matter |
| Id-6 | ??CH 2CH 3 | ?Br | Oily matter |
| Id-7 | ??CH 2CH 3 | ??C≡CSi(CH 3) 3 | Oily matter |
| Id-8 | ??CH 2CH 3 | ??H | Oily matter |
Table 5
Ph=phenyl table 6 following formula: compound
Ph=phenyl table 7 following formula: compound
Ph=phenyl table 8 following formula: compound
| The compound sequence number | ??R 1 | ??R 2 | ?R 3 | ?G | ?R 40 | ?R 41 | ?R 42 | ?R 43 | Physicochemical constant |
| ??Ie-1 | ??CH 3CH 2 | ??Ph | ??CH 3O | ??H | ??H | ??H | ??-(CH 2) 2- | ??m.p.196-197℃ | |
| ??Ie-2 | ??CH 3CH 2 | ??Ph | ??CH 3O | ??H | ??CH 3CH 2 | ??H | ??H | ??H | ??m.p.133-135℃ |
| ??Ie-3 | ??CH 3CH 2 | ??Ph | ??CH 3O | ??H | ??CH 3 | ??CH 3 | ??H | ??H | ??m.p.139-145℃ |
| ??Ie-4 | ??CH 3CH 2 | ??Ph | ??CH 3O | ??H | ??CH 3 | ??CH 3 | ??H | ??H | ??m.p.119℃ |
| ??Ie-5 | ??CH 3CH 2 | ??Ph | ??CH 3O | ??C(O)- ??C(CH 3) 3 | ??CH 3CH 2 | ??H | ??H | ??H | Crystallization |
| The compound sequence number | R 1 | R 2 | ?R 3 | ?G | Physicochemical constant |
| If-1 | ?CH 3CH 2 | ?Ph | ?CH 3O | ?H | ?m.p.184-188℃ |
| The compound sequence number | R 1 | R 2 | ?R 3 | ?G | Physicochemical constant |
| Ig-1 | ?CH 3CH 2 | ?Ph | ?CH 3O | ?H | ?m.p.147-149℃ |
| The compound sequence number | R 1 | R 2 | ?R 3 | ?R | ?G | Physicochemical constant |
| Ih-1 | -OCH 3 | ?Ph | ?C 2H 5 | ?OH | ?C(O)C(CH 3) 3 | 1H?NMR(CDCl 3, 300MHz) δ=7.6 (d, 2H); 7.42 (t, 2H); 7.34 (t, 1H); 7.1 (s, 1H); 6.88 (s, 1H); 4.2-3.14 (m, 6H); 3.8 (2s, 3H); 2.67 (m, 2H); 2.05 (m, 2H); 1.2 (m, 3H); 1.1 (m, 9H) (isomer mixture) |
| ??Ih-2 | ??CH 2CH 3 | ??Ph | ??OCH 3 | ??H 3C-O- ??CH 2CH 2-O- | ??C(O)C(CH 3) 3 | ?? 1H?NMR(CDCl 3， ??300MHz)δ＝7.6 ??(d，2H)；7.42(t， ??2H)；7.34(t，1H)； ??7.1(s，1H)；6.88(s， ??1H)；4.5(m， ??0.26H)；4.2(m， ??0.17H)；4.0-3.3 |
| (m, 8H); 3.8 (bs, 3H); 3.4 (2s, 3H); 3.2 (m, 0.5H); 2.7 (m, 2H), 2.3-1.85 (m, 2H), 1.2 (m, 3H), 1.1 (m, 9H) (isomer mixtures) | ||||||
| ?Ih-3 | ?CH 2CH 3 | ?Ph | CH 2- CH 3 | ?H 3C-O- CH 2CH 2-O- | C(O)C(CH 3) 3 | |
| ?Ih-4 | ?CH 2CH 3 | ?Ph | Ethynyl | H 3C-O- CH 2CH 2-O- | C(O)C(CH 3) 3 | |
| ?Ih-5 | ?CH 2CH 3 | ?Ph | CH 2- CH 3 | ?H 3C-CH 2-O- CH 2CH 2-O- | C(O)C(CH 3) 3 | |
| ?Ih-6 | ?CH 3 | ?Ph | CH 3 | ?H 3C-O- CH 2CH 2-O- | C(O)C(CH 3) 3 |
The Ph=phenyl
Embodiment B 2: postemergence herbicide activity
Unifacial leaf and dicotyledonous test plants are sowed in the flowerpot that standard soil is housed.When test plants is in 2-to 3-leaf during the phase, with the water suspending agent of test compounds (by the wettable powder (embodiment F 3 of WO97/34485, b) preparation) or the emulsion of test compounds (by the missible oil of WO97/34485 (embodiment F 1, c) preparation) with the optimum concn (spray application of 500 premium on currency/ha).In the greenhouse under the optimum, further cultivate test plants then.
After test duration 2-3 week, with 9 grades (1=all kills, and 9=is effect not) degree evaluation test result.Grade 1-4 (particularly 1-3) expression is good to extraordinary weeding activity.
Table B2:
In this test, formula I compound shows very strong weeding activity.Formula I compound according to other embodiment preparation of WO97/34485 obtains same result.
| Compound | Amount of application (g/ha) | Oat | Rye grass | Herba Setariae Viridis | Sinapsis alba |
| Ib-1 | ?2000 | ?1 | ?2 | ?1 | ?2 |
| Ib-4 | ?2000 | ?1 | ?3 | ?1 | ?2 |
| Ib-2 | ?2000 | ?3 | ?3 | ?1 | ?2 |
| Ia-33 | ?2000 | ?2 | ?2 | ?1 | ?2 |
| Ib-66 | ?2000 | ?1 | ?2 | ?1 | ?2 |
| Ia-4 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ia-5 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-9 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-10 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ia-1 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ia-2 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ia-6 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ia-7 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-13 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-14 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-28 | ?2000 | ?1 | ?2 | ?1 | ?2 |
| Ia-8 | ?2000 | ?2 | ?1 | ?1 | ?2 |
| Ib-20 | ?2000 | ?2 | ?2 | ?1 | ?2 |
| Ib-21 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-69 | ?2000 | ?2 | ?2 | ?1 | ?2 |
| Ib-18 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ib-19 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| Ie-1 | ?2000 | ?1 | ?1 | ?1 | ?2 |
| If-1 | ?2000 | ?1 | ?1 | ?1 | ?3 |
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH164499 | 1999-09-07 | ||
| CH1644/99 | 1999-09-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1377358A true CN1377358A (en) | 2002-10-30 |
Family
ID=4215283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00813584A Pending CN1377358A (en) | 1999-09-07 | 2000-09-05 | Novel herbicides |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1230245A2 (en) |
| CN (1) | CN1377358A (en) |
| AU (1) | AU7514600A (en) |
| CA (1) | CA2382432A1 (en) |
| HU (1) | HUP0202844A3 (en) |
| PL (1) | PL356456A1 (en) |
| WO (1) | WO2001017973A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1863806B (en) * | 2003-08-14 | 2010-06-16 | 拜尔农作物科学股份公司 | 4-biphenyl-substituted pyrazolidine-3, 5-dione derivatives |
| CN101039926B (en) * | 2004-10-27 | 2010-10-27 | 辛根塔参与股份公司 | Method for preparing [1,4,5]-oxodiazepine derivatives |
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| TWI316939B (en) * | 2001-12-18 | 2009-11-11 | Syngenta Participations Ag | Process for the preparation of organic compounds |
| HUP0402592A2 (en) * | 2002-01-22 | 2005-04-28 | Syngenta Participations Ag | Phenyl substituted heterocyclic compounds useful as herbicides |
| DE10311300A1 (en) | 2003-03-14 | 2004-09-23 | Bayer Cropscience Ag | New 2-alkoxy-4-halo-6-alkylphenyl-substituted (hetero)cyclic ketoenols, useful as total or selective herbicides and pesticides, e.g. insecticides, acaricides and nematocides for plant protection |
| DE10326386A1 (en) * | 2003-06-12 | 2004-12-30 | Bayer Cropscience Ag | N-heterocyclyl-phenyl-substituted cyclic ketoenols |
| DE10331675A1 (en) | 2003-07-14 | 2005-02-10 | Bayer Cropscience Ag | Hetaryl-substituted pyrazolidinedione derivatives |
| DE10337496A1 (en) * | 2003-08-14 | 2005-04-14 | Bayer Cropscience Ag | 4-biphenyl-4-substituted-pyrazolidine-3,5-dione |
| DE102004014620A1 (en) | 2004-03-25 | 2005-10-06 | Bayer Cropscience Ag | 2,4,6-phenyl-substituted cyclic ketoenols |
| DE102004035133A1 (en) | 2004-07-20 | 2006-02-16 | Bayer Cropscience Ag | Selective insecticides based on substituted cyclic ketoenols and safeners |
| DE102004044827A1 (en) | 2004-09-16 | 2006-03-23 | Bayer Cropscience Ag | Iodine-phenyl-substituted cyclic ketoenols |
| DE102005059469A1 (en) | 2005-12-13 | 2007-06-14 | Bayer Cropscience Ag | Insecticidal compositions having improved activity |
| DE102006007882A1 (en) | 2006-02-21 | 2007-08-30 | Bayer Cropscience Ag | New cyclic keto enol derivatives useful for controlling animal pests and/or unwanted plant growth |
| NZ577571A (en) | 2006-12-14 | 2012-03-30 | Syngenta Participations Ag | 4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones as novel herbicides |
| GB0710223D0 (en) | 2007-05-29 | 2007-07-11 | Syngenta Ltd | Novel Herbicides |
| GB0712653D0 (en) | 2007-06-28 | 2007-08-08 | Syngenta Ltd | Novel herbicides |
| GB0715454D0 (en) | 2007-08-08 | 2007-09-19 | Syngenta Ltd | Novel herbicides |
| GB0715576D0 (en) | 2007-08-09 | 2007-09-19 | Syngenta Ltd | Novel herbicides |
| NZ585790A (en) * | 2007-12-13 | 2012-02-24 | Syngenta Ltd | 4-Phenylpyrane-3,5-diones, 4-phenylthiopyrane-3,5-diones and 2-phenylcyclohexane-1,3,5-triones as herbicides |
| GB0812310D0 (en) | 2008-07-03 | 2008-08-13 | Syngenta Ltd | Novel herbicides |
| GB0900641D0 (en) | 2009-01-15 | 2009-02-25 | Syngenta Ltd | Novel herbicides |
| GB0901086D0 (en) | 2009-01-22 | 2009-03-11 | Syngenta Ltd | Novel herbicides |
| GB0901835D0 (en) | 2009-02-04 | 2009-03-11 | Syngenta Ltd | Novel herbicides |
| GB0901834D0 (en) | 2009-02-04 | 2009-03-11 | Syngenta Ltd | Novel herbicides |
| CN103641709B (en) | 2009-03-11 | 2017-08-25 | 拜耳知识产权有限责任公司 | The ketone enol replaced by haloalkyl methylene phenyl |
| DE102010008644A1 (en) | 2010-02-15 | 2011-08-18 | Bayer Schering Pharma Aktiengesellschaft, 13353 | Cyclic ketoenols for therapy |
| JP5842594B2 (en) | 2010-12-27 | 2016-01-13 | 住友化学株式会社 | Pyridazinone compounds, herbicides containing them, and harmful arthropod control agents |
| AR087008A1 (en) | 2011-06-22 | 2014-02-05 | Syngenta Participations Ag | DERIVATIVES OF N-OXI-PIRAZOLO-TRIAZEPINA-DIONA |
| US9089137B2 (en) | 2012-01-26 | 2015-07-28 | Bayer Intellectual Property Gmbh | Phenyl-substituted ketoenols for controlling fish parasites |
| ES2902985T3 (en) | 2017-12-05 | 2022-03-30 | Syngenta Participations Ag | Chemical procedure for the synthesis of herbicidal pyrazolidinedione compounds |
| CN117603156A (en) * | 2023-11-22 | 2024-02-27 | 浙江工业大学 | A method for synthesizing pinoxaden intermediate N-acetyl-[1,4,5]-oxadiazepane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2280504A (en) * | 1938-03-03 | 1942-04-21 | Gen Aniline & Film Corp | Process for producing compounds of the diaryl series |
| US4252817A (en) * | 1975-03-12 | 1981-02-24 | Sandoz Ltd. | Substituted-2,3-dihydrobenzofuran-2-ones |
| JPS56125338A (en) * | 1980-03-07 | 1981-10-01 | Nippon Shinyaku Co Ltd | Phenylacetic acid derivative |
| WO1992016510A1 (en) * | 1991-03-19 | 1992-10-01 | Ciba-Geigy Ag | Novel herbicidally, acaricidally and insecticidally active compounds |
| JP2003502403A (en) * | 1999-06-16 | 2003-01-21 | シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト | New intermediate |
| KR100752941B1 (en) * | 1999-06-16 | 2007-08-30 | 신젠타 파티서페이션즈 아게 | Method for preparing herbicide derivative |
-
2000
- 2000-09-05 WO PCT/EP2000/008657 patent/WO2001017973A2/en not_active Ceased
- 2000-09-05 HU HU0202844A patent/HUP0202844A3/en unknown
- 2000-09-05 PL PL00356456A patent/PL356456A1/en not_active Application Discontinuation
- 2000-09-05 CA CA002382432A patent/CA2382432A1/en not_active Abandoned
- 2000-09-05 EP EP00964108A patent/EP1230245A2/en not_active Withdrawn
- 2000-09-05 AU AU75146/00A patent/AU7514600A/en not_active Abandoned
- 2000-09-05 CN CN00813584A patent/CN1377358A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1863806B (en) * | 2003-08-14 | 2010-06-16 | 拜尔农作物科学股份公司 | 4-biphenyl-substituted pyrazolidine-3, 5-dione derivatives |
| CN101039926B (en) * | 2004-10-27 | 2010-10-27 | 辛根塔参与股份公司 | Method for preparing [1,4,5]-oxodiazepine derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7514600A (en) | 2001-04-10 |
| HUP0202844A3 (en) | 2003-01-28 |
| PL356456A1 (en) | 2004-06-28 |
| WO2001017973A3 (en) | 2001-05-10 |
| EP1230245A2 (en) | 2002-08-14 |
| CA2382432A1 (en) | 2001-03-15 |
| WO2001017973A2 (en) | 2001-03-15 |
| HUP0202844A2 (en) | 2002-12-28 |
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