CN1061221A - The aryl alkylsulfonyl pyrazoles of the replacement of weeding - Google Patents
The aryl alkylsulfonyl pyrazoles of the replacement of weeding Download PDFInfo
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- CN1061221A CN1061221A CN91108858.XA CN91108858A CN1061221A CN 1061221 A CN1061221 A CN 1061221A CN 91108858 A CN91108858 A CN 91108858A CN 1061221 A CN1061221 A CN 1061221A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- 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
- C07D231/18—One oxygen or sulfur atom
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
The present invention relates to the aryl pyrazole compound of some replacement, contain their herbicidal composition, the method for using the method for their weedings and preparing described compound.
Description
The FIELD OF THE INVENTION that this paper proposes is the herbicidal compound about above-mentioned title common name, the method that contains their composition and prepare described compound.
The 3-of various replacements and 5-arylpyrazole compounds are known in the literature, and these compounds have various uses, for example as chemical intermediate, medicine and weedicide.
In the prior art, the aryl pyrazole compound of these replacements is to have various substituent compounds on the aryl of compound and/or pyrazoles part.For example, known such compound: the aryl moiety in these compounds is that replace or unsubstituted phenyl, substituting group wherein is an alkyl, cycloalkyl, alkaryl, halogen, trifluoromethyl, the furyl that the heterocyclic radical of heterocyclic radical or replacement such as thienyl or alkyl replace, pyridyl, pyrimidyl urea etc., and pyrazolyl is replaced by following groups on all places of its N or carbon atom: alkyl, halogen, alkoxyl group, heterocyclic radical, S(O)
nThe R group, wherein n is 0-2, R is various groups those groups as replacing on aryl or pyrazoles part.
The existing compound of the above-mentioned type of useful as herbicides generally need use up to per hectare 5 or 10 kilograms or more substantial ratio just can reach the purpose that is enough to controlling weeds.Therefore, the purpose of this invention is to provide the new arylpyrazole compounds of a class, these compounds are to various weeds, be included in various crops, particularly granule cereal and/or drilling crop, have unique high phytotoxicity as narrow leaf among wheat, barley, corn, soybean, the peanut etc. and broadleaf weeds, but have the security of height.
The present invention relates to the compound of weeding activity, contain these compound compositions, the method for preparing their method and use their weedings.
Wherein:
R
1Be hydrogen, use R
4The C that group replaces arbitrarily
1-5Alkyl is used C
1-4The C that alkyl replaces arbitrarily
3-8Cycloalkyl or cycloalkenyl group;
R
2Be to use R
4The C that group replaces arbitrarily
1-5Alkyl;
R
3It is hydrogen or halogen;
R
4Be hydrogen, C
1-8Alkyl, haloalkyl, alkylthio, alkoxyalkyl or multi-alkoxy alkyl, C
3-8Cycloalkyl, cycloalkenyl group, cycloalkylalkyl or cycloalkenyl alkyl, C
2-8Alkenyl or alkynyl; Formamyl, halogen, amino, nitro, cyano group, hydroxyl contains 1-4 O, S(O)
mAnd/or the heteroatomic C of N
4-10Heterocycle, C
6-12Aryl, aralkyl or alkaryl ,-CXYR
8,-CXR
9,-CH
2OCOR
10,-YR
11,-NR
12R
13, or any two R
4Group can by saturated and/or undersaturated carbon,
And/or the heteroatoms bonding forms and to have the nearly heterocycle of 9 links, and this heterocycle can be by any described R
4Group replaces, or by with any described R
4The described R that does not comprise itself that group replaces
4Group or R
8-13Group replaces; Its condition is as described two R
4Group passes through heteroatoms
Bond is fashionable, and described heterocycle has six links at least;
X is O, S(O)
m, NR
14Or CR
15R
16;
Y is O or S(O)
mOr NR
17;
R
8-R
17Be described R
4In the group one;
M is 0-2;
N is 0-5.
Preferred subclass is a formula II compound in the arylpyrazole based compound that the present invention replaces:
Wherein:
R
1, R
2And R
3Suc as formula defining in the I:
R
5Be described R independently
3In the group one;
R
6And R
7Described independently R
4In the group one, or in conjunction with forming the heterocycle that has 9 joints nearly and contain O, N and/or S atom, this ring can be had the nearly alkyl of 4 carbon atoms, and haloalkyl, alkoxyl group, alkenyl or alkynyl replace; Its condition is as described two R
6And R
7Group passes through heteroatoms
Bond is fashionable, and described heterocycle has six links at least.
The particularly preferred compound of the present invention is a formula III compound:
Wherein:
R
1And R
2Be C
1-5Alkyl;
R
3And R
5Be hydrogen, bromine, chlorine or fluorine;
R
6Be R
5Group or nitro;
R
7Be R
4Group;
R
6And R
7By-OCH
2(C=O)-N-(R
4)-bond is closed and is formed the condensed six-ring.
The compound that is more preferably according to the formula III is these compounds, wherein:
R
1And R
2It is methyl;
R
3Be hydrogen, bromine or chlorine;
R
5Be chlorine or fluorine;
R
6Be chlorine, fluorine or nitro;
R
7Be the YR that defines in the formula I
11Group; Or
R
6And R
7By-OCH
2(C=O)-the N-(proyl)-in conjunction with forming the condensed six-ring.
A preferred class comprises following compounds according to the present invention:
4-chloro-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
6-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-7-fluoro-4-(2-proyl)-2H-1, the 4-benzoxazine-3-(4H)-ketone
(5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate, 1-methyl ethyl ester
(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate, 1-methyl ethyl ester
2-(5-(4-bromo-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate, and
2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate
Another aspect of the present invention is about the compound of preparation according to formula I-III, the method for the intermediate of their precursor and starting raw material, and the each side of these methods will discuss in more detail hereinafter.
Others of the present invention are about the herbicidal composition that contains formula I-III compound and use these compositions to come the herbicidal methods of control of undesirable weeds.
Within the scope of the invention, be to make the aryl pyrazole compound of the replacement of formula I-III can be mixed with the composition that contains the common weedicide of other herbicidal compound conduct further, other herbicidal compound such as monoacetylaniline, thiocarbamate, urea, sulfonylurea, imidazolone, phenylformic acid and derivative thereof, phenyl ether, glyphosate salt etc.
In these herbicidal formulations, also can comprise required and suitable other annexation.As be used for the toxinicide (safener) of weedicide, plant disease controlling agent such as mycocide, sterilant, nematocides and other agricultural chemicals.
Term used herein " alkyl ", " alkenyl ", " alkynyl " when with independent or when using with the form of compound word such as haloalkyl, halogenated alkenyl, alkoxyl group, alkoxyalkyl etc., is meant the group that comprises straight or branched.Preferred alkyl is the low alkyl group with 1 to 4 carbon atom, and preferred alkenyl and alkynyl are the groups with 2 to 4 carbon atoms.
Term " haloalkyl " is meant the alkyl that replaces with one or more halogens (chlorine, bromine, iodine or fluorine) atom; Preferred this type of group is group, particularly halogenated methyl such as the trifluoromethyl with 1 to 4 carbon atom.In multi-haloalkyl, all halogens can be identical or various halogens.
Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl group and the cycloalkenyl alkyl of typical indefiniteness comprise following groups:
The propyl group of methyl, ethyl, isomery, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.; Vinyl, allyl group, crotyl, methylallyl, the butenyl of isomery, pentenyl, hexenyl, heptenyl, octenyl; Ethynyl, the proyl of isomery, butynyl, pentynyl, hexin base etc.; The alkoxyl group of abovementioned alkyl, many alkoxyl groups, alkoxyalkyl and multi-alkoxy alkyl analogue, as methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy and hexyloxy and corresponding many alkoxyl groups and alkoxyalkyl, as methoxymethoxy, methoxy ethoxy, oxyethyl group methoxy base, ethoxy ethoxy, methoxymethyl, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, the propoxy-methyl, the isopropoxy methyl, butoxymethyl, the isobutoxy methyl, the tert.-butoxy methyl, the pentyloxy methyl, hexyloxy methyl etc., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, the cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl etc.; Cyclopentenes, tetrahydrobenzene and suberene with isomery of one or two unsaturated link(age)s; Typical aryl, aralkyl and alkaryl comprise phenyl, the tolyl of isomery and xylyl, benzyl, naphthyl etc.
Typical one, two and tri haloalkyl partly comprise: chloromethyl, chloroethyl, brooethyl, bromotrifluoromethane, iodomethyl, iodine ethyl, chloropropyl, bromopropyl, the iodine propyl group, 1,1-dichloromethyl, 1,1-two brooethyls, 1,1-two chloropropyls, 1, the 2-dibromopropyl, 2,3-dibromopropyl, 1-chloro-2-bromotrifluoromethane, 2-chloro-3-bromopropyl, trifluoromethyl, trichloromethyl etc.
Typical heterocyclic group comprises: the alkyl thiadiazolyl group; Piperidyl (piperidyl); The piperidyl alkyl; The dioxolanyl alkyl; Thiazolyl; The alkyl thiazolyl; Benzothiazolyl; The halogeno-benzene benzothiazolyl; Furyl; The furyl that alkyl replaces; Furyl alkyl; Pyridyl; Alkylpyridyl; Wan Ji oxazolyl; The tetrahydrofuran base alkyl; 3-cyano thiophene base; The thienyl alkyl; The thienyl that alkyl replaces; 4,5-polyalkylene thienyl; 2,3-or 4-piperidyl; Alkyl 2-, 3-or 4-piperidyl; Pyridyl; Two-or tetrahydro pyridyl; The alkyl tetrahydro morpholinyl; The alkyl morpholine base; The azabicyclo nonyl; The diazacyclo alkyl, benzo alkyl pyrrolidine base; Oxazolidinyl; Full Qingization oxazolidinyl; Wan Ji oxazolidinyl; Fu Nan Ji oxazolidinyl; Sai fen Ji oxazolidinyl, Bi Ding Ji oxazolidinyl, Mi Ding Ji oxazolidinyl, benzoxazole alkyl, C
3-7Volution alkyl oxazolidinyl, the alkylamino alkenyl; Alkylideneimino; Pyrrolidyl; Piperidone base; Perhydro-azepines base; Perhydro-azocine base; Pyrazolyl; The pyrazoline base; Piperazinyl; Perhydro--carotene 1, the 4-diaza
Base; Quinolyl, isoquinolyl; Two-, four-and perhydro-quinolyl or isoquinolyl; Indyl and two-and the perhydro-indyl, described heterocyclic group can be used suc as formula the group that defines in the I and replace.
Term used herein " acceptable salt on the agricultural " (by the defined compound of above-mentioned general formula) is meant that in water medium ionization forms the positively charged ion of described compound or negatively charged ion and the cationic salt or the salt of negatively charged ion and corresponding salt easily, these salts do not have deleterious effect to the herbicidal performance of giving weedicide, and make the preparation of herbicidal composition not have unfavorable problem at aspects such as the use that mixes, suspends, stablizes, uses machine, packings.
" herbicidally effective amount " is meant the amount that the efficient part to undesirable plant that is acted on or weeds produces significant damage or damages needed weedicide.Though do not have rigid and certain regulation, but viewpoint from commerce, requirement can be removed 80-85% or more weeds, and is although in most cases effective inhibition of weed growth is significantly less than this level, all the more so the plant of particularly very deleterious for some, antiweed.
Can prepare aptly with the whole bag of tricks as described below according to compound of the present invention.
Generally speaking, the entire method of preferred preparation formula I-III compound is preferably from for obtaining necessary intermediate, moment precursor and each required method steps of final product of above-mentioned general formula consider.From this viewpoint, should comprise at least ten three main method stepss, these will be described below.The product of formula I-III can prepare with the flow process of " method I-X III " generally as described below.Certainly, also can expect conspicuous for a person skilled in the art various changes.Specific embodiment will be described in following embodiment 1-27.
In series of method steps as described below, the substituent various symbols such as the R of definition group
1-R
17, X, Y etc. have identical meaning when being used for definition I-III compound, except as otherwise noted or limit.
Method 1
Present method has been described the preparation of important midbody compound, and these compounds are used for the entire method flow process of preparation formula I-III compound, R
3For the following formula B compound intermediate of H can prepare with this method step.
Preparation is according to the suitable methyl phenyl ketone that replaces from formula A known in the art (not) of method of formula B compound, this method can be carried out in the mixture of any anhydrous solvent or these solvents, preferred solvent is methyl-sulphoxide, toluene, benzene etc., () methyl phenyl ketone that replaces does not preferably use alkali metal alcoholates such as potassium tert.-butoxide with highly basic such as alkalimetal hydride or alkali metal alcoholates processing.Alkaline mixt is handled with dithiocarbonic anhydride.Temperature of reaction in-100 ℃ to 100 ℃ scopes, preferred-78 ℃ to 50 ℃.After adding dithiocarbonic anhydride, react available alkylogen, the alkyl dihalo-, the alkyl sodium sulfate ester, sulfonic acid dialkyl or other suitable alkylating agent are handled, and preferably the reagent that uses is methyl-iodide.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, intermediate 1-(is replaced by the dilute with water reaction mixture)-3, two (the alkylthio)-2-propylene of 3--1-ketone is separated, then with isolating product as crystallization or solvent extraction method.If be necessary that product can be used the ordinary method purifying.This intermediate cyclisation is obtained formula B compound, and this cyclisation can be in any suitable solvent be handled with the hydrazine of hydrazine or replacement and is finished, and preferably uses alkyl hydrazine, temperature of reaction in-78 ℃ to 150 ℃ scopes, preferred 10 ℃ to 100 ℃.Reaction times can be selected to the scope in several weeks from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
Intermediate 1-(replaces in that hydrazine is added to)-3, under the situation of two (the alkylthio)-2-propylene of 3--1-ketone, the product pyrazoles can use alkylogen, and alkyl sulfonate esters or the processing of other suitable alkylating agent obtain formula B compound.In the case, by with alkylating agent such as methyl-iodide, bromotoluene, allyl bromide 98, processing above-claimed cpd such as methyl-sulfate and obtain formula B product.Preferred solvent is a methyl-sulphoxide, acetone, dimethyl formamide ， diox etc.Temperature of reaction in-78 ℃ to 150 ℃ scopes, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
Be used for compound 4 by method for preparing table 1,9,10 and 11 2-chloro-4-fluoro-5-methoxyacetophenone is prepared by 2-chloro-4-fluoroanisole, and it is with methods known in the art [C.A.Buehler and D.E.Pearson, " organic synthesis summary " (Survey of Organic Synthesis) pp.285-382, Wiley-Inter-Seience, New YorK, 1970] make by 2-chloro-4-fluoro-phenol.At room temperature handle 2-chloro-4-fluoroanisole and obtain 2-fluoro-4-chloro-5-methoxybenzaldehyde with titanium tetrachloride and dichloromethyl methyl ether.Follow with ordinary method oxidation known in the art by handling, make 2-fluoro-4-chloro-5-methoxybenzaldehyde be converted into 2-fluoro-4-chloro-5-methoxyacetophenone with methyl Ge Liya.
Above-mentioned 2-fluoro-4-chloro-5-methoxyacetophenone and similar precursor thereof, 2-fluoro-4-chloro-5-methoxybenzaldehyde, and the method for preparing them is found by the other contriver (Bruce C.Hamper and Kindrick L.Les-chinsky) that transferee of the present invention employs.
The table I has been listed the exemplary embodiments that is prepared compound by the method I.
Table 1
The physical data of 3-aryl-5-methylthio group pyrazoles
Compound number R
1R
5R
6R
7Physical data
Mp(℃) or nD(25 ℃)
1 CH
3F H F light yellow oil
2 CH
3F Cl CH
390.0
3 CH
3F Cl H 44.0-45.0
4 CH
3F Cl OCH
350.0-51.0
5 CH
3H H CF
3nD1.5533（25℃）
6 CH
3F OCH
3H nD1.6036（25℃）
7 CH
3Cl Cl H 90.0
8 H F H F 88.0
9 H F Cl OCH
3133-135
10 CH（CH
3）
2F Cl OCH
366-67
11 Et F Cl OCH
3nD1.5989（25℃）
12 CH
3F F H nD1.5820
These compounds those formula category-B compounds as shown in the table I can be used as the starting raw material for preparing various other compounds, also can be used as the intermediate of preparation according to formula II compound.For example, the compound of table in the I can be on the 3-position of pyrazoles halo and make the representative new compound shown in the table II.
The table II
The physical data of 3-aryl-4-halo-5-methylthio group pyrazoles
Compound number R
1R
5R
6R
7Physical data
Mp (℃) or nD (25 ℃)
14 CH
3F H F nD1.5791
15 CH
3F NH
2F 123.0-124.0
16 CH
3F NH
2OCH
3nD1.6212
17 CH
3F C1 F nD1.5937
18 CH
3F C1 OCH
387.0-88.0
19 CH
3F C1 CH
383.0
20 CH
3F OCH
3H nD1.5943
21 H F C1 OCH
3151.0-152.5
The method II
Present method has been described the important step that comprises oxidation-type B compound formula I compound, and the principal character of this method step is the sulfide derivatives of formula B is transformed the S that obtains formula I compound, S-dioxide derivative.Therefore, should understand that oxidation system described below only is representational, but from the principle, can finish the S of the formula B sulfide derivatives of expection that any suitable method that the S-dioxide derivative transforms all can consider to be used in this to the formula I.
The sulfo-pyrazoles of the replacement of oxidation-type B can obtain corresponding formula I sulfonyl pyrazole.Any inert solvent all can be used for this reaction, as long as the carrying out of its not obvious obstruction reaction.These solvents include but are not limited to: organic acid, mineral acid, hydrocarbon, halohydrocarbon, aromatic hydrocarbon, ether or sulfone.Suitable oxygenant comprises but is not limited to molecular oxygen, organic and inorganic peroxide, organic peracid, inorganic oxide; Preferred reagent is hydrogen peroxide, peroxybenzoic acid, basic metal periodate, alkali metal permanganate etc.Temperature of reaction in-78 ℃ to 150 ℃ scopes, preferred 10 ℃ to 100 ℃.Reaction times can be selected to the scope in several weeks from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, by the dilute with water reaction mixture product is separated, then with isolating product as methods such as crystallization or solvent extractions.If be necessary that product can be used the ordinary method purifying.
The method III
In the description of present method, a class R
3For the formula D product of halogen is by corresponding R
3The halogenation that for hydrogen and P is 0 or 2 formula C compound prepares.
Any inert solvent all can be used for this reaction, as long as the carrying out of its not obvious obstruction reaction.These solvents include but is not limited to organic acid, mineral acid, hydrocarbon, halohydrocarbon, aromatic hydrocarbon, ether and sulfide, sulfoxide or sulfone.The halogenating agent that is suitable for above-mentioned reaction comprises bromine, chlorine, N-bromo-succinimide, N-neoprene imide, sulfuryl chloride, 1,3-two chloro-5,5-dimethyl hydantion etc.When using some halogenating agent, preferably use organo-peroxide or light as catalyzer.The amount of halogenating agent can be from equimolar amount to excessive.Temperature of reaction in-100 ℃ to 150 ℃ scopes, preferred 10 ℃ to 100 ℃.Reaction times can be selected from several minutes to several weeks or in the scope of longer time, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, by the dilute with water reaction mixture product is separated, then with isolating product as methods such as crystallization or solvent extractions.If be necessary that product can be used the ordinary method purifying.
The method IV
This section is described and is begun to prepare R by formula (1) compound
4One of group is the method for formula I (formula E) compound of nitro.
The mixture of nitrating agent such as concentrated nitric acid, nitrosonitric acid, nitric acid and the vitriol oil, alkyl nitrate ester selected and acetyl nitric ether all are applicable to this reaction.Solvent such as mineral acid, organic solvent such as diacetyl oxide or methylene dichloride, and the mixture of water or these solvents all can use.Nitrating agent can equimolar amount or excessive use.Temperature of reaction in-100 ℃ to 150 ℃ scopes, preferred-10 ℃ to 100 ℃.Reaction times can be selected to several days the scope from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, by the dilute with water reaction mixture product is separated, then with isolating product as methods such as crystallization or solvent extractions.If be necessary that product can be used the ordinary method purifying.
The method V
In the description of present method, a class formula G product (i.e. a class formula II compound) is that the replacement by the Z group of corresponding formula F compound prepares, and wherein Z is previously defined R
4Any suitable leavings group of group.
The preparation of formula G product is in the presence of alkali, in any suitable solvent, carries out with processing formula F compounds such as alkoxide, sulfo-alkoxide, amine etc. or alcohol, mercaptan, amine.Preferred solvent is methyl-sulphoxide, acetone, dimethyl formamide, diox, water etc.But alkali organic bases (as trialkylamine or other organic amine) or mineral alkali (alkaline carbonate such as salt of wormwood or yellow soda ash).Temperature of reaction in-100 ℃ to 150 ℃ scopes, preferred-10 ℃ to 100 ℃.Reaction times can be selected to the scope in several weeks from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
The method VI
In the description of present method, various formula I compounds (represented as shown in the formula J) are by formula H compound (R
4One of group is the formula I compound of nitro) preparation.
A, in the first step of this two-step approach, formula H compound reduction is obtained the sulfonamide derivatives of formula J, one of them R
4Group is amino.The reductive agent that is suitable for acidic medium includes but is not limited to metal such as iron, zinc or tin.Reaction solvent comprises organic or mineral acid such as acetate or hydrochloric acid, can concentrated acid solution or the use of dilute aqueous soln form.Temperature of reaction in 0 ℃ to 150 ℃ scope, preferred 10 ℃ to 100 ℃.Reaction times can be selected to the scope in several weeks from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.
After reaction is finished, by the dilute with water reaction mixture product is separated, this product can be with separating as methods such as crystallization or solvent extractions, if be necessary that product can be used the ordinary method purifying.
On the other hand, formula H compound can reduce by catalytic hydrogenation.For the catalytic hydrogenation that can carry out under normal pressure or high pressure, appropriate catalyst comprises Raney nickel, palladium/carbon, platinum black, the palladium on any carrier, palladous oxide, platinum black etc.Solvent comprises any inert solvent of not obvious obstruction reaction, and these solvents comprise alcohol, ether etc.After reaction is finished, isolate product by filtration and concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
B, the following step by present method are converted into various functional groups such as halogen (preferably), cyano group, hydroxyl etc. with the amino of steps A product.Any suitable solvent all can use in this reaction, but preferably uses anhydrous solvent such as anhydrous acetonitrile.Comprise copper halide with mantoquita, cuprous halide, the mixture of copper halide and cuprous halide or other mantoquita and their mixture are also used the solution or the pulpous state liquid of nitroso-group alkyl ester or other organic sub-nitrate such as nitrite tert-butyl treatment step A product.Temperature of reaction in 0 ℃ to 150 ℃ scope, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
Another working method that amino is converted into the various functional groups that comprise the described group of leading portion comprises uses various ordinary methods such as Sandmeyer, reactions such as Meerwein, and these reactions use diazonium salt as intermediate.
The method VII
In the description of present method, R wherein
4One of group is that the formula I compound of YH is by one of them R
4Group is YR
11And R
11It or not the formula I compound of hydrogen.
This reaction can be in any suitable solvent or pure reagent carry out with the form of solution or suspension.Can use Lewis acid as (but being not limited to) BBr
3, AlCl
3Deng, or the mineral acid such as dense hydrochloric acid, sulfuric acid, Hydrogen bromide or its aqueous solution etc.Temperature of reaction in 0 ℃ to 150 ℃ scope, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
The method VIII
In the description of present method, R wherein
4One of group is YR
11And R
11The formula I compound that is not hydrogen is by one of them R
4Group is the formula I compound of YH.
In the typical embodiments of this method, the preparation of the product of above-mentioned definition is handled starting raw material with alkylating agent or acylating agent and is carried out, alkylating agent such as alkylogen or alkyl sulfonate esters, methyl-iodide for example, allyl bromide 98, propargyl bromide, methyl benzenesulfonate etc.This reaction can be with or without catalyzer in the mixture of any suitable solvent or solvent, have or alkali-free in the presence of carry out.Preferred solvent is a methyl-sulphoxide, acetone, dimethyl formamide ， diox etc.But alkali organic bases (as trialkylamine or other organic amine) or mineral alkali (alkaline carbonate such as salt of wormwood or yellow soda ash).Temperature of reaction in 0 ℃ to 150 ℃ scope, preferred 10 ℃ to 100 ℃.Reaction times can be selected to the scope in several weeks from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
The method IX
Present method has been described by corresponding formula K compound formula M compound (formula II compound, wherein R
7Be YCH
2-n(R
18)
nCOYR
20).Radicals R
13-20As the front for as described in R
4The definition of group.
A, in the first step of this two-step approach, pass through YR
19The hydrolysis of group makes formula K compound be converted into formula L compound.This reaction can have or catalyst-free in the mixture of any suitable solvent or solvent, carries out in the presence of alkali or acid.Preferred solvent is water, pure, diox, methyl-sulphoxide, acetone, dimethyl formamide etc.Under the basic hydrolysis situation, preferred mineral alkali such as alkali metal hydroxide.For acid hydrolysis, can use mineral acid such as concentrated hydrochloric acid or sulfuric acid, organic acid or these sour mixtures.Temperature of reaction in 0 ℃ to 150 ℃ scope, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, by the dilute with water reaction mixture and/or with acid treatment solvent (under the situation of basic hydrolysis) product is separated, this product can be with separating as methods such as crystallization or solvent extractions.If be necessary that product can be used the ordinary method purifying.
B, make the product of steps A be converted into formula M compound by esterification or the reaction that forms acid amides.It can directly be finished by compound L or by an alkali metal salt of compound L.This esterification can be carried out in the presence of mineral acid (as sulfuric acid) with the excessive alcohol corresponding to the purpose ester.Amide derivatives can prepare by handling compound L with required amine in pure reagent or suitable solvent.The reaction of esterification or formation acid amides also can be carried out in the presence of inert solvent and dewatering agent.
On the other hand, the product of steps A can be converted into acyl halide or acid anhydride and use alcohol or the amine processing.The preparation of acyl halide be at halogenating agent as (but being not limited to) sulphinyl chlorine, phosphorus pentachloride, oxalyl chloride etc. exist down, carry out when being with or without inert solvent.Any inert solvent that reaction is not had influence all can use.In order to promote this reaction, can add the amine alkali such as the triethylamine of catalytic amount, pyridine or dimethyl formamide or the like.Temperature of reaction at-20 ℃ to the boiling spread of solvent for use.Reaction times can be from several minutes to 48 hour, and it depends on the amount and the temperature of reaction of used reagent.After reaction is finished, from reaction product, remove excessive halogenating agent and solvent by evaporation or distillation.The product acyl halide can directly be handled with amine or alcohol, or uses the usual method purifying.
Handle acyl halide with alcohol or amine and obtain formula M compound.Any inert solvent all can use, and in order to promote this reaction, can add the amine alkali such as the triethylamine of catalytic amount, pyridine or dimethyl formamide etc.Temperature of reaction at-20 ℃ to the boiling spread of solvent for use.Reaction times can be from several minutes to 48 hour, and it depends on the amount and the temperature of reaction of used reagent.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
The method X
Present method has been described compound (formula II compound, the wherein R by formula N compound formula O, P, Q, R, S or T
7Substituting group is alkyl, haloalkyl, carboxyl aldehyde, carboxylic acid or carboxylic acid derivative such as the previously defined CXYR of alkyl, replacement
8Or CXR
9).Radicals R
21And R
22As the front for R
4The definition of group, X
1And X
2It is halogen.The schema of method is as follows.
In the first step of this method, formula N compound is converted into formula O or Q compound or these mixture of products.Any inert solvent all can be used for this reaction, as long as the carrying out of its not obvious obstruction reaction.These solvents include but is not limited to organic acid, mineral acid, hydrocarbon, halohydrocarbon, aromatic hydrocarbon, ether and sulfide, sulfoxide or sulfone.The halogenating agent that is suitable for above-mentioned reaction comprises bromine, chlorine, N-bromo-succinimide, N-neoprene imide, sulfuryl chloride etc.With some halogenating agent the time, preferably use organo-peroxide or light as catalyzer.The amount of halogenating agent can be from waiting mole to excessive.Temperature of reaction in-100 ℃ to 150 ℃ scopes, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, by the dilute with water reaction mixture product or all products are separated, with isolating product as methods such as crystallization or solvent extractions.If be necessary that product can have the ordinary method purifying.
Replace halogen group X with suitable nucleophilic reagent
i, make formula O compound be converted into the formula P-compound.The preparation of formula P product be in the presence of alkali in any suitable solvent, carry out with processing formula O compounds such as alkoxide, sulfo-alkoxide, amine, alkyl or aryl negatively charged ion etc. or alcohol, mercaptan, amine.Preferred solvent is methyl-sulphoxide, acetone, dimethyl formamide, diox etc.But alkali organic bases (as trialkylamine or other organic amine) or mineral alkali (alkaline carbonate such as salt of wormwood or yellow soda ash).Temperature of reaction in 0 ℃ to 150 ℃ scope, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, isolate product by filtration and/or concentrated reaction mixture.If be necessary, product can carry out purifying with ordinary method such as extraction, crystallization, column chromatography etc.
The preparation of formula R product is that the acid hydrolysis of through type Q compound is carried out.In order to carry out acid hydrolysis, formula Q compound is handled with excessive mineral acid example hydrochloric acid or sulfuric acid, the excessive greatly sulfuric acid of preferred use.Temperature of reaction 0 ℃ to the boiling spread of inert solvent, preferred 10 ℃ to 100 ℃.Reaction times can extremely be selected in the scope in several weeks from several minutes, and it depends on the amount of reagent, temperature of reaction etc.After reaction is finished, by the dilute with water reaction mixture product or all products are separated, then with isolating product as methods such as crystallization or solvent extractions.If be necessary that product can be used the ordinary method purifying.
Obtain formula S compound by oxidation-type R compound.Any suitable inert solvent all can be used for this reaction, and it comprises hydrocarbon, aromatic hydrocarbon, pyridine and derivative, water etc.The available oxygenant comprises (but being not limited to) superoxide such as potassium permanganate or potassium bichromate.Temperature of reaction 0 ℃ to the boiling spread of inert solvent, preferred 10 ℃ to 100 ℃.Reaction times can be selected to the scope in several weeks from several minutes, and it depends on the amount, temperature of reaction etc. of reagent.After reaction is finished, by the dilute with water reaction mixture product or all products are separated, then with isolating product as methods such as crystallization or solvent extractions.If be necessary that product can be used the ordinary method purifying.
The final step of this method comprises any various ordinary methods of using the preparation carboxylic acid derivative, and formula S compound is converted into formula T compound.This method steps is esterification or the reaction that forms acid amides, and it can directly be finished by compound S or by an alkali metal salt of compound S.This esterification can be carried out in the presence of mineral acid (as sulfuric acid) with the excessive alcohol corresponding to the purpose ester.Amide derivatives can prepare by handling compound S with required amine in pure reagent or suitable solvent.The reaction of esterification or formation acid amides also can be carried out in the presence of inert solvent and dewatering agent.
On the other hand, formula S compound can be converted into acyl halide or acid anhydride and use alcohol or the amine processing.The preparation of acyl halide be at halogenating agent as (but being not limited to) sulphinyl chlorine, phosphorus pentachloride, oxalyl chloride etc. exist down, carry out when being with or without inert solvent.Any inert solvent that reaction is not had influence all can use.In order to promote this reaction, can add the amine alkali such as the triethylamine of catalytic amount, pyridine or dimethyl formamide or like that.Temperature of reaction at-20 ℃ to the boiling spread of solvent for use.Reaction times can be from several minutes to 48 hour, and it depends on the amount and the temperature of reaction of used reagent.After reaction is finished, from reaction product, remove excessive halogenating agent and solvent by evaporation or distillation.The product acyl halide can directly be handled and available usual method purifying with amine or alcohol.
Acyl halide is obtained formula T compound with alcohol or amine processing.Any inert solvent can be used, and can add catalytic amount amine alkali such as triethylamine, and pyridine or dimethyl formamide etc. are to promote this reaction.Temperature of reaction-20 ℃ to the solvent for use boiling spread, the reaction times does not coexist according to used reaction volume and temperature of reaction and selects in several minutes to the 48 hour scope.After reaction is finished, by filtering and/or the concentrated reaction mixture separated product.If desired, product can pass through as extraction, crystallization, ordinary method purifying such as column chromatography.
The method XI
This part has been narrated by formula I compound and has begun to prepare wherein R
4One of group is represented the formula I compound of thiol (formula U).
In this method, desired compound obtains formula U compound by reduction subsequently by elder generation's preparation halogen sulphonyl intermediate and obtains.Only otherwise influence reaction process, any solvent can be used, as halohydrocarbon, and ether, alkyl nitrile, mineral acid etc.Excessive chlorsulfonic acid not only can be preferably as the reagent of preparation chlorosulfonyl intermediate but also can be preferably as solvent.Temperature of reaction at 25 ℃ to the solvent for use boiling spread.Reaction times is according to amount of reagent, and temperature of reaction etc. can be selected to a few week scope at several minutes.After reaction is finished, separate this product or multiple product by the thin up reaction mixture, and isolate product by crystallization or solvent extraction method.If desired, product can be used the ordinary method purifying.
Reduction halogen sulphonyl intermediate can be at the inert solvent, comprise inorganic or organic acid in carry out, these acid are as acetate or hydrochloric acid, and can concentrated acid solution or rare aqueous solution form use.
The reductive agent that is adapted in the acidic medium comprises, but is not restricted to metal such as iron, zinc or tin.Reaction solvent comprises that temperature of reaction 0 ℃ to 150 ℃ scope, is preferably 10 ℃ to 100 ℃.Reaction times is according to amount of reagent, and temperature of reaction etc. can be selected to a few week scope at several minutes.
After reaction was finished, product separated by the dilute with water reaction mixture, and passed through as crystallization or solvent-extracted method separated product.If desired, product ordinary method purifying.
The method XII
In this method steps, formula V compound (R wherein
2Represent CH
2R
23, R
23Representative as the preceding R that limits
4The formula I compound of one of group) by R wherein
2The formula I compound of represent methylidene.
Any solvent all can use, but must be anhydrous, not with the water effect, and disturbance reponse process not.Preferential anhydrous ether such as tetrahydrofuran (THF), ether or the polyethers of using.Temperature of reaction usually-100 ℃ between the boiling point of solvent for use, be preferably-78 ℃ to 25 ℃.Originally, formula I compound highly basic such as metal alkylide, metal hydride, processing such as metal amide are used alkylating agent such as alkylogen, processing such as alkyl sulfonic ester subsequently.Reaction times is according to amount of reagent, and temperature of reaction etc. can be selected to a few week scope at several minutes.
After reaction is finished, by dilute with water reaction mixture separated product, by as crystallization or solvent-extracted method separated product.If desired, product ordinary method purifying.
Method X III
This method steps has been narrated formula W compound and has been converted to formula X or Y compound, residue R
24Representative as the preceding R that limits
4One of group, and n represents 0 or 1 integer.
In this reactions steps, the nitro of reduction-type W compound obtains sulfonamide derivatives, separates this derivative or according to R
24Residue character, directly cyclisation obtains formula X and Y product.Sometimes, above-mentioned reaction needed is carried out at elevated temperatures, so that promote the cyclic action of amine intermediate.The reductive agent that is suitable in acidic medium comprises, but is not restricted to metal such as iron, zinc or tin.Reaction solvent comprises organic or mineral acid, as acetate or hydrochloric acid, and can concentrated acid solution or the use of dilute aqueous soln form.Temperature of reaction is preferably 10 ℃ to 100 ℃ in 0 ℃ to 150 ℃ scope.Reaction times, temperature of reaction etc. can be selected to several all scopes at several minutes according to the reaction reagent amount.
After reaction is finished, by dilute with water reaction mixture separated product with as crystallization or solvent-extracted method separated product.If desired, product ordinary method purifying.
Perhaps, formula W compound reduces by catalytic hydrogenation.Catalytic hydrogenation can be carried out under normal pressure or elevated pressure, and suitable catalyzer comprises Raney nickel, palladium on carbon, and palladium black is stated from the palladium on any suitable carrier, palladous oxide, platinum, platinum black etc.Solvent comprises any inert solvent, if the reaction of not obvious obstruction, as alcohol, ether etc.After reacting completely, by filtering and the concentrated reaction mixture separated product.If desired, product is used as ordinary method purifying such as extraction, crystallization, column chromatographys.
The following example 1-27 has illustrated the concrete operations embodiment for preparing representative The compounds of this invention.In the following embodiments, carrying out sorbing material used in the chromatogram purification is silicon-dioxide.
Embodiment 1-3 has described the specific embodiments of method I, is used to prepare the midbody compound of final product of the present invention.
Embodiment 1
(A) all appts flame drying under nitrogen.In 10 minutes to 5.4g(0.18mol) add 14.04g(0.09mol in the pulpous state liquid of 80% oil dispersion NaH in the anhydrous DMSO of 150ml) 2,5-difluoro acetophenone (buy on the market).Can be observed gas evolution, the reaction be cooled to 15 ℃ and in 15 minutes, add 5.4ml(0.09mol) CS
2Maintain the temperature at 15 ℃ and pilot-gas effusion.At CS
2After adding, under 20 ℃, add 11.1ml(0.018mol immediately) methyl iodide.Stirring at room reaction 2 hours.With in the reaction mixture impouring 500ml ice and stirred 1 hour.Cross filter solid, washing and dry air.The residuum chromatogram purification is made eluent with the hexane that contains 20% ethyl acetate, obtains 19.8g(85%) 1-(2, the 5-difluorophenyl)-3,3-two (methylthio group)-2-propylene-1-ketone, yellow solid, mp105.5 ℃;
Perhaps, for the method described in the step (A), also can use the mixture of dry solvent, as the mixture of DWSO and THF.
Ultimate analysis C
11H
10F
2O
1S
2:
Calculated value: C, 50.75; H, 3.87; S, 24.63.
Measured value: C, 50.85; H, 3.86; S, 24.75.
(B) under 24 ℃, in 15 minutes to 4.0g(0.0154mol) add 1.65ml(0.031mol in the 50ml acetonitrile pulpous state liquid of step (A) product) methyl hydrazine, reflux solution 6 hours.Coupling vacuum stripping solution, residuum are eluent through chromatogram purification with the hexane that contains 10% ethyl acetate, obtain 3.05g(82%) 3-(2, the 5-difluorophenyl)-1-methyl-5-(methylthio group)-the 1H-pyrazoles, be light yellow oil.
Ultimate analysis C
11H
10F
2N
2S
1:
Calculated value: C, 54.99; H, 4.20; N, 11.66; S, 13.34.
Measured value: C, 55.03; H, 4.26; N, 11.55; S, 13.38.
Embodiment 2
Present embodiment has been narrated 3-(2, the 5-difluorophenyl)-1-methyl-5-methylthio group-1H-pyrazoles and 5-(2, the 5-difluorophenyl)-preparation of 1-methyl-3-methylthio group-1H-pyrazoles isomer mixture.
A. at 24 ℃, in 3 minutes to 5.2g1-(2, the 5-difluorophenyl)-3, add the 1.3ml anhydrous hydrazine in the 50ml acetonitrile solution of 3-two (methylthio group)-2-propylene-1-ketone.Be reflected at 95 ℃ of heating 1 hour.The vacuum concentration reactant, resistates is used anhydrous MgSO with ether dissolution and washing
4Drying, and vacuum concentration.Residuum hexane recrystallization obtains 4.14g(94%) 3-(2, the 5-difluorophenyl)-the 5-(methylthio group)-1H-pyrazoles white solid, mp88 ℃.
Ultimate analysis C
10H
8F
2N
2S
1:
Calculated value: C, 53.09; H, 3.56; N, 12.38; S, 14.17.
Measured value: C, 53.12; H, 3.55; N, 12.40; S, 14.15.
B. will contain 3.44g steps A product, 2.2g K
2CO
3, and the 75ml acetone pulpous state liquid of 1.0ml methyl iodide spend the night in 25 ℃ of stirrings.Solution is with the dilution of 300ml cold water and with ethyl acetate extraction three times.Acetic acid ethyl acetate extract salt water washing, anhydrous MgSO
4Drying, and vacuum concentration.Resistates is through chromatogram purification, with the hexane that contains 10% ethyl acetate is eluent, obtain 2.97g(85%) 3-(2, the 5-difluorophenyl)-1-methyl-5-methylthio group-1H-pyrazoles (analytical data is seen embodiment 1) and 0.35g(10%) 5-(2, the 5-difluorophenyl)-1-methyl-3(methylthio group)-the 1H-pyrazoles, be light yellow oily body, n
25D 1.5731.
Ultimate analysis C
11H
10F
2N
2S
1:
Calculated value: C, 54.99; H, 4.20; N, 11.66.
Measured value: C, 54.83; H, 4.19; N, 11.85.
Embodiment 3
Present embodiment has been described 3-(2, the 4-difluorophenyl)-1-methyl-5-(methylthio group)-preparation of 1H-pyrazoles.
All glassware flame dryings.To churned mechanically potassium tert.-butoxide (43g, add in anhydrous tetrahydro furan 0.38mol) (600ml) solution 2,4 difluorobenzene ethyl ketone (30g, 0.192mol), solution heat release to 40 ℃, and under this temperature, stirring 30 minutes.Solution is cooled to 0 ℃ then, and (adding speed is no more than 1 ℃ for making temperature of reaction for 11.6ml, 0.192mol) solution to add dithiocarbonic anhydride.After adding, be reflected at 0 ℃ and stirred 15 minutes, (23.6g 0.38mol), and makes the solution temperature rising be no more than 1 ℃ to add methyl-iodide subsequently.Cooling solution no longer, stirred solution reaches till 10 ℃ up to solution temperature, and this moment is with in the reaction soln impouring 1L frozen water.Collect two parts of yellow solid product that can leach, obtain ultimate production 48.1g(96% productive rate) the dithio ketal.With the dithio ketal (47g 0.180mol) is dissolved in the acetonitrile (500mol), and once add whole methyl hydrazines (21g, 0.45mol).Reflux solution 24 hours, coupling vacuum stripping goes out most of acetonitrile then.Extracted with diethyl ether will also be used in the remaining liq impouring frozen water, organic phase is with salt water washing three times and use anhydrous magnesium sulfate drying, remove whole volatile matters and obtain the 37.77g(87% productive rate) 3-(2, the 4-difluorophenyl)-1-methyl-5-(methylthio group)-the 1H-pyrazoles, be amber oil.
1HNMR（CDCl
3）ppm：7.82（q，J＝6.6，1H），6.78（m，2H），6.55（d，J＝3.6，1H），3.83（S，3H），2.34（S，3H）。
Ultimate analysis C
11H
10F
2N
2S
1:
Calculated value: C, 54.99; H, 4.20; N, 11.66.
Measured value: C, 55.06; H, 4.23; N, 11.60.
Embodiment 4,5 and 6 has illustrated the concrete operations embodiment of method II.
Embodiment 4
Present embodiment has been described 3-(2, the 5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
With 2.66g(0.011mol) the 50ml dichloromethane solution of the product of embodiment 1 step (B) is cooled to-5 ℃.In reaction mixture, add 7.6g(0.022mol) the 100ml dichloromethane solution of 50-60% metachloroperbenzoic acid, and at room temperature stir and spend the night.This solution washs with the saturated sodium bicarbonate solution that contains 5% Sulfothiorine, with after washing, and anhydrous MgSO
4Drying, and vacuum concentration.Resistates methylcyclohexane recrystallization obtains 2.8g(93%) 3-(2, the 5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles, be white solid, mp126-127 ℃.
Ultimate analysis C
11H
10F
2O
2S
1:
Calculated value: C, 48.53; H, 3.70; N, 10.29; S, 11.78.
Measured value: C, 48.61; H, 3.70; N, 10.26; S, 11.71.
Embodiment 5
Present embodiment is described 5-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-the 3-(methylsulfonyl)-preparation of 1H-pyrazoles.
To 1.12g5-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-the 3-(methylthio group)-the 1H-pyrazoles adds 3.2g oxone heating heterogeneous mixture to 85 ℃ in the solution of 30ml glacial acetic acid and 15ml alcohol mixture, after 2 hours with in its impouring frozen water.The mixture that forms dichloromethane extraction three times, and organic extract is concentrated, obtain the oily residuum.With among the dense HCl and the 10%NaOH aqueous solution of oily body residuum, obtain solid precipitation, with its collection and washing, obtain 0.60g(48%) 5-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-the 3-(methylsulfonyl)-the 1H-pyrazoles.By using the methanol recrystallization, obtain analyzing with yellow crystalline solid sample; Mp213-216 ℃ (decomposition).
Ultimate analysis C
11H
10N
2O
3F
1:
Calculated value: C, 43.36; H, 3.31; N, 9.19; S, 10.52.
Measured value: C, 43.51; H, 3.33; N, 9.10; S, 10.44.
Embodiment 6
Present embodiment has been described 4-chloro-3-(2-fluoro-4-methoxyl group-phenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
At 0 ℃, to 4-chloro-3-(2-fluoro-4-p-methoxy-phenyl)-1-methyl-5-(methylthio group)-(3.5g divides mono chloro benzene formic acid between the short run adding to the 1H-pyrazoles in methylene dichloride 0.0122mol) (150ml) solution.Stirring at room reaction 20 hours, organic phase is with twice of the saturated sodium thiosulfate solution extraction that contains 50% saturated sodium bicarbonate solution then.The organism anhydrous magnesium sulfate drying, and vacuum removes volatile matter, obtains yellow solid, mp=75 ℃.
Ultimate analysis C
12H
12F
1N
2O
3S
1Cl
1:
Calculated value: C, 45.22; H, 3.79; N, 8.79.
Measured value: C, 45.49; H, 3.77; N, 8.69.
The concrete operations embodiment of embodiment 7 and 8 narration method III.
Embodiment 7
Present embodiment has been described 4-chloro-3-(2,5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
At 25 ℃, with 2.25g(8.2mmol) embodiment 4 products are dissolved in the 40ml glacial acetic acid and in 50 minutes and blast 1.1g(16.4mmol) chlorine, stirring reaction 45 minutes.In reaction soln impouring 300ml frozen water, and use extracted with diethyl ether.Ether extraction liquid is washed anhydrous MgSO with saturated sodium bicarbonate solution
4Drying, and vacuum concentration.Residuum is made eluent through chromatogram purification with the hexane that contains 30% ethyl acetate, obtains 1.35g(84%) 4-chloro-3-(2, the 5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazoles white solid, mp77 ℃.
Ultimate analysis C
11H
9Cl
1F
2N
2O
2S
1:
Calculated value: C, 43.08; H, 2.96; N, 9.13; S, 10.45; Cl, 11.56.
Measured value: C, 43.16; H, 2.97; N, 9.12; S, 10.39; Cl, 11.49.
Embodiment 8
Present embodiment has been described 4-chloro-3-(2-fluoro-4-p-methoxy-phenyl)-1-methyl-5-(methylthio group)-preparation of 1H-pyrazoles.
At 0 ℃, to 3-(2-fluoro-4-p-methoxy-phenyl)-1-methyl-5-(methylthio group)-(4g 0.015mol) adds 1,3-two chloro-5 in the solution among ether (30ml) and 1 Glacial acetic acid to the 1H-pyrazoles, the 5-T10 (1.77g, 0.009mol).Stirring at room reaction 1 hour is then in the impouring ice.The organism extracted with diethyl ether, the salt water washing, anhydrous magnesium sulfate drying and coupling vacuum stripping obtain yellow oil, in the time of 25 ℃, n
25D=1.5943.
Ultimate analysis C
12H
12F
1N
2O
1S
1Cl
1:
Calculated value: C, 50.26; H, 4.22; N, 9.77.
Measured value: C, 49.84; H, 4.13; N, 9.16.
The concrete implementation and operation embodiment of embodiment 9 and 10 illustration method IV.
Embodiment 9
Present embodiment has been described 4-chloro-3-(2,5-two fluoro-4-nitrophenyls)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
Under 24 ℃, with 1.5g(4.9mmol) 4-chloro-3-(2, the 5-difluorophenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles slowly is added in the 25ml nitrosonitric acid.Being reflected at 30 ℃ stirred 30 minutes.Reactant is inclined in 300ml ice.Filter pulpous state liquid, and filter cake water thorough washing and dry air.Solid methylcyclohexane recrystallization obtains 1.13g(66%) 4-chloro-3-(2,5-two fluoro-4-nitrophenyls)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles, be beige solid, mp147 ℃.
Ultimate analysis C
11H
8Cl
1F
2N
3O
4S
1:
Calculated value: C, 37.56; H, 2.29; N, 11.95; S, 9.12.
Measured value: C, 37.60; H, 2.29; N, 11.98; S, 9.10.
Embodiment 10
Present embodiment has been described 4-chloro-3-(4-chloro-2-fluoro-5-nitrophenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
To 3g(0.0093mol) 4-chloro-3-(4-chloro-2-fluorophenyl)-1-methyl-5-(methylsulfonyl)-be added dropwise to the mixture of the 1ml concentrated nitric acid and the 3ml vitriol oil in the 3ml concentrated sulfuric acid solution of 1H-pyrazoles, again mixture was stirred 2 hours at 25 ℃.Then with in the reaction mixture impouring ice-water and use extracted with diethyl ether.Then organic extract liquid is used 100ml NaCl solution washing three times, dry (MgSO
4), filter and concentrate, obtain 2.3g(67%) 4-chloro-3-(4-chloro-2-fluoro-5-nitrophenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazoles yellow solid.Chromatogram purification (10% EtOAC/CH
2Cl
2) obtain analytic sample, mp111-115 ℃.
Ultimate analysis C
11H
8N
3O
4Cl
2F
1S
1+ 1/4EtOAC:
Calculated value: C, 36.45; H, 2.60; N, 10.85.
Measured value: C, 36.39; H, 2.26; N, 10.91.
Embodiment 11 and 12 has illustrated the concrete operations embodiment of method V.
Embodiment 11
Present embodiment has illustrated 4-chloro-3-(2-fluoro-5-methoxyl group-4-nitrophenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
With 4.8g(0.0137mol) product of embodiment 9,1.9g(0.014mol) K
2CO
3, and 5ml methyl alcohol was in forming slurries under 25 ℃ in 50ml DMSO, 45 ℃ of stirring reactions 8 hours.Cooling reaction, with the dilution of 100ml cold water, and with ethyl acetate extraction four times.Acetic acid ethyl acetate extract salt water washing, anhydrous MgSO
4Drying, and coupling vacuum stripping.Resistates ethyl acetate/hexane recrystallization obtains 4.21g(84%) 4-chloro-3-(2-fluoro-5-methoxyl group-4-nitrophenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles, be yellow solid, mp178.5-180 ℃.
Ultimate analysis C
12H
11Cl
1F
1N
3O
5S
1:
Calculated value: C, 39.62; H, 3.05; N, 11.55; S, 8.81.
Measured value: C, 39.58; H, 2.98; N, 11.54; S, 8.59.
Embodiment 12
Present embodiment has illustrated 5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-4-fluoro-N-(1-methylethyl)-preparation of 2-N-methyl-p-nitroaniline.
To 4-chloro-3-(2; 5-two fluoro-4-nitrophenyls)-1-methyl-5-(methylsulfonyl)-1H-pyrazoles (7.6g; 0.0218mol) N-Methyl pyrrolidone (50ml) solution in add Isopropylamine (1.94g; 0.0328mol); (4.5g is 0.0328mol) with catalytic amount cupric fluoride (II) for salt of wormwood.In 60 ℃ of reacting by heating two hours and complete by the TLC detection reaction.Reaction is with the ethyl acetate dilution and with organism salt water washing three times; anhydrous magnesium sulfate drying; and vacuum is removed volatile matter; behind ethanol/methylcyclohexane recrystallization; obtain 8.4g(98%) 5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-4-fluoro-N-(1-methylethyl)-the 2-N-methyl-p-nitroaniline; be orange solids, mp152 ℃.
Ultimate analysis C
14H
16Cl
1F
1N
4O
4S
1:
Calculated value: C, 43.03; H, 4.13; N, 14.34.
Measured value: C, 43.09; H, 4.09; N, 14.36.
Embodiment 13
Present embodiment has been described 4-chloro-3-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles, be the specific embodiments of method V 1.
(A) with 3.3g(9.1mmol) 4-chloro-3-(2-fluoro-5-methoxyl group-4-nitrophenyl)-1-methyl-5-(methylsulfonyl)-the 100ml Glacial acetic acid pulpous state liquid of 1H-pyrazoles is heated to 80 ℃ under nitrogen atmosphere, and portion-wise addition 1.5g(27mmol) iron powder handles.After 20 minutes, cooling mixture also passes through Celite 85 ℃ of reactions
Filter.Resulting solution is with the dilution of 250ml water and with ethyl acetate extraction three times.The organic extract liquid water, saturated NaHCO
3Solution and water washing, MgSO
4Dry and concentrated, obtain the 3.1g brown solid.
(B) with 3.0g(9.0mmol) the 70ml anhydrous acetonitrile of step (A) product uses 0.9g(9.0mmol at 25 ℃) CuCl and 1.8g(13.1mmol) CuCl
2Handle.In 5 minutes, in reaction mixture, add 2.4ml(18mmol) 90% nitrite tert-butyl solution.28 ℃ the reaction 1 hour after, the vacuum concentration reaction mixture.Reaction residual is with acetic acid ethyl dissolution and use 10%HCl solution washing three times, salt solution washed twice, anhydrous MgSO
4Drying, and vacuum concentration.Residuum is through chromatogram purification, and the hexane that contains 50% ethyl acetate is an eluent, obtains 2.64g(83%) 4-chloro-3-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles, be white solid, mp127.5 ℃.
Ultimate analysis C
12H
11Cl
2F
1N
2O
3S
1:
Calculated value: C, 40.81; H, 3.14; N, 7.93; S, 9.08; Cl, 10.08.
Measured value: C, 40.94; H, 3.14; N, 7.88; S, 8.97; Cl, 19.95.
The concrete operations embodiment of embodiment 14-16 illustration method VII.
Embodiment 14
Present embodiment explanation 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-preparation of 4-fluoro-N-2-propenyl aniline.
With 1g(0.0023mol) N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl]-2; 2; the 2-trifluoroacetamide; 0.97g(0.007mol) salt of wormwood, 25ml dry DMF and 0.85g(0.007mol) solution of allyl bromide 98 stirred 24 hours at 70 ℃.This solution dilutes with EtOAc, 100ml5%HCl washing three times, dry (MgSO
4), filter and concentrate, obtain the 0.9g reddish oil.Be dissolved in oil in the 20ml methyl alcohol and add 3ml10%NaOH.This mixture stirred 8 hours at 25 ℃.Reaction mixture dilutes with EtOAc, uses 100ml NaCl solution washing three times, dry (MgSO
4), filter and concentrate, obtain the 0.8g reddish oil.Chromatogram purification (CH
2Cl
2), obtain 0.6g(69%) 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-4-fluoro-N-2-propenyl aniline, be yellow oil, n
25D=1.5956.
Ultimate analysis C
14H
14N
3O
2Cl
2F
1S
1:
Calculated value: C, 44.64; H, 3.73; N, 11.11.
Measured value: C, 44.66; H, 3.68; N, 10.85.
Embodiment 15
Present embodiment has illustrated N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl]-preparation of Toluidrin
To 0.5g(0.001mol) N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl]-the N-(methylsulfonyl) add 2ml10%NaOH in the 20ml methanol solution of Toluidrin.This mixture stirred 4 hours at 25 ℃.Reaction mixture dilutes with EtOAC, with 100ml5%HCl washing three times, and dry (MgSO
4), filter and concentrate, obtain 0.2g(48%) N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl] Toluidrin, be isabelline solid.Chromatogram purification (EtOAc) obtains analytic sample, mp165-166 ℃.
Ultimate analysis C
12H
12N
3O
4Cl
2F
1S
2+ 1/4EtOAC:
Calculated value: C, 35.18; H, 3.24; N, 9.65.
Measured value: C, 35.09; H, 2.97; N, 9.90.
Embodiment 16
Present embodiment has illustrated 4-chloro-3-(4-chloro-2-fluoro-5-hydroxy phenyl)-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
With 1.15g(3.25mmol) 4-chloro-3-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-1-methyl-5-(methylsulfonyl)-the 30ml dichloromethane solution of 1H-pyrazoles is cooled to 0 ℃, and slowly dripped 4ml1MBBr in 5 minute
3Dichloromethane solution (4.0mmol) is handled.Stirring at room solution spends the night.The solution with water washed twice is used anhydrous MgSO
4Drying, and vacuum concentration.Residuum hexane recrystallization obtains 1.1g(100%) 4-chloro-3-(4-chloro-2-fluoro-5-hydroxy phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles, be beige solid, mp190.5 ℃.
Ultimate analysis C
11H
9Cl
2F
1N
2O
3S
1:
Calculated value: C, 38.95; H, 2.67; N, 8.26.
Measured value: C, 38.93; H, 2.67; N, 8.43.
Embodiment 17,18,19 and 20 has illustrated the concrete operations embodiment of method VIII.
Embodiment 17
Present embodiment has illustrated 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-4-fluoro-N-(1-methylethyl)-preparation of aniline.
With 0.5g(0.0015mol) 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 5ml anhydrous DMF solution of 4-fluoroaniline and 2ml 2-iodopropane stirred 6 hours at 75 ℃, stirred 2-1/2 days at 25 ℃ then.Reaction mixture dilutes with EtOAc, uses the 50ml5%HCl washed twice, dry (MgSO
4), filter and concentrate, obtain the 0.5g reddish oil.Chromatogram purification (methylene dichloride) obtains 0.25g(44%) 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-4-fluoro-N-(1-methylethyl)-the aniline red solid, mp118 ℃-121 ℃.
Ultimate analysis C
14H
15N
3O
2Cl
2F
1S
1+ 1/2H
2O:
Calculated value: C, 43.20; H, 4.40; N, 10.79;
Measured value: C, 42.88; H, 4.02; N, 10.70.
Embodiment 18
Present embodiment has illustrated N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl] preparation of alanine ethyl ester.
With N-[2-chloro-5-[4-chloro-2-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl] ethanolic soln of L-Ala and the Acetyl Chloride 98Min. of catalytic amount stirred 18 hours at 25 ℃.This solution dilutes with EtOAc, washes with water, and with 100ml solution of potassium carbonate washed twice, dry (MgSO
4), filter and concentrate, obtain the 0.5g yellow oil.Chromatogram purification (CH
2Cl
2) obtain 0.17g(20%) N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl] the alanine ethyl ester yellow oil.
1HNMR（400MHz，CDCl
3）d1.2（S，3H），1.48（d，3H），3.23（S，3H），3.8（q，1H），4.15（q，2H），4.18（S，3H），4.7（bs，1H），6.6（d，1H），7.1（d，1H）ppm：;
19FNMR（360MHZ，CDCl
3）d，128（S，1F）ppm。
Ultimate analysis C
16H
18N
3O
4Cl
2F
1S
1:
Calculated value: C, 43.85; H, 4.14; N, 9.59.
Measured value: C, 43.90; H, 4.11; N, 9.52.
Embodiment 19
Present embodiment has illustrated N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl]-the N-(methylsulfonyl) preparation of Toluidrin.
To 0.5g(0.0015mol) 2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-add 0.33g(0.0033mol in the 20ml dichloromethane solution of 4-fluoroaniline) triethylamine, add 0.37g(0.0033mol subsequently) methylsulfonyl chloride.Mixture stirred 18 hours at 25 ℃.Reaction mixture dilutes with EtOAc, with 100ml5% HCl washing three times, and dry (MgSO
4), filter and concentrate, obtain 0.7g(94%) N-[2-chloro-5-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-the 4-fluorophenyl]-the N-[methylsulfonyl)-Toluidrin, be pale solid.Chromatogram purification (EtOAc) obtains analytic sample, mp234-237 ℃.
Ultimate analysis C
13H
14N
3O
6Cl
2F
1S
3+ 1/4EtOAC:
Calculated value: C, 32.17; H, 3.14; N, 8.18.
Measured value: C, 32.05; H, 2.86; N, 8.48.
Embodiment 20
Present embodiment has illustrated 4-chloro-3-(4-chloro-2-fluoro-5-(2-third alkynyloxy group) phenyl-1-methyl-5-(methylsulfonyl)-preparation of 1H-pyrazoles.
With 0.87g(2.5mmol) 4-chloro-3-(4-chloro-2-fluoro-5-hydroxy phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazoles, 0.4g(3.0mmol) K
2CO
3, and 0.3ml(3.0mmol) mixture of propargyl bromide forms slurries in 25 ℃ in 10mlDMSO.Being reflected at 45 ℃ stirred 16 hours.To react cooling, with the dilution of 100ml cold water, and with ethyl acetate extraction four times.Acetic acid ethyl acetate extract salt water washing, anhydrous MgSO
4Drying, and coupling vacuum stripping.Residuum is eluent through chromatogram purification with the hexane that contains 50% ethyl acetate, obtains 0.93g(96%) 4-chloro-3-(4-chloro-2-fluoro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles, be brown solid, mp135 ℃.
Ultimate analysis C
14H
11Cl
2F
1N
2O
3S
1:
Calculated value: C, 44.58; H, 2.94; N, 7.43.
Measured value: C, 44.75; H, 3.08; N, 7.36.
Embodiment 21 and 22 has illustrated the concrete operations embodiment of method IX.
Embodiment 21
Present embodiment has illustrated 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-the 4-fluorophenoxy) preparation of propionic acid.
To 3.77g(8.6mmol) 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-the 4-fluorophenoxy)-ethyl propionate 20ml water and 20ml 1, add 3.5ml(8.6mmol in the pulpous state liquid in the 4-diox) 10%NaOH solution.Afterreaction liquid became limpid in 30 minutes.And TLC show the reaction finish.Cooling solution is also regulated PH to 3 with dense HCl.The reactant ethyl acetate extraction.Extraction liquid washes with water, anhydrous MgSO
4Drying, and vacuum concentration.Residuum hexane recrystallization obtains 2.9g(83%) 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-the 4-fluorophenoxy)-propionic acid, be white solid, mp56 ℃.
Ultimate analysis C
14H
13Cl
2F
1N
2O
5S
1:
Calculated value: C, 40.80; H, 3.19; N, 6.81.
Measured value: C, 40.87; H, 3.24; N, 6.69.
Embodiment 22
Present embodiment has illustrated 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1-pyrazole-3-yl)-the 4-fluorophenoxy)-preparation of N-methyl propanamide.
To 1.17g(5.9mmol) 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-the 4-fluorophenoxy)-in 3 minutes, add 0.8ml(9.6mmol in the 10ml dichloromethane solution of propionic acid) oxalyl chloride; beginning has gas evolution; when waiting not have gas evolution, till adding 1 DMF and solution stirring being stopped to gas evolution.Solution is stripped to dried under vacuum.Residuum is dissolved in the 5mlTHF and in 0 ℃, in 5 minutes it is added in the 10ml40% aqueous methylamine solution.Stirring at room reaction mixture 30 minutes.In the solution impouring 150ml cold water and use ethyl acetate extraction.Acetic acid ethyl acetate extract with the salt water washing is repeatedly used anhydrous MgSO
4Drying, and coupling vacuum stripping.Solid obtains 0.96g(80% with methylcyclohexane/re-crystallizing in ethyl acetate) 2-(2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-the 4-fluorophenoxy)-the N-methyl propanamide, be white solid, mp178 ℃.
1HNMR（CDCl
3）ppm：1.55（d，3H），2.81（d，3H）;3.23（S，3H），4.17（S，3H），4.64（q，3H），6.65（br，1H），6.97（d，1H），7.22（d，1H）。
Ultimate analysis C
15H
16Cl
2F
1N
3O
4S
1:
Calculated value: C, 42.46; H, 3.80; N, 9.90.
Measured value: C, 42.60; H, 3.68; N, 9.86.
Embodiment 23 and 24 has illustrated the concrete operations embodiment of method X.
Embodiment 23
Present embodiment has illustrated (((2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-4-fluorophenyl) methyl) sulfo-) preparation of ethyl acetate.
At 25 ℃, with 1.25g(3.0mmol) the 3-(5-(brooethyl)-4-chloro-2-fluorophenyl)-4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazoles, 0.5g(3.3mmol) K
2CO
3And 0.4ml(3.3mmol) ethyl bromoacetate forms slurries in 15ml acetone.Being reflected at 20 ℃ stirred 8 hours.In the reactant impouring 150ml water, filter and dry air.Solid methylcyclohexane recrystallization obtains 1.2g(93%) (((2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-4-fluorophenyl) methyl) sulfo-) the ethyl acetate white solid, mp110 ℃.
Ultimate analysis C
16H
17Cl
2F
1N
2O
4S
2:
Calculated value: C, 42.20; H, 3.76; N, 6.15.
Measured value: C, 42.25; H, 3.72; N, 6.18.
Embodiment 24
Present embodiment has illustrated 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-preparation of 4-fluoro-N-methyl-benzamide.
In 3 minutes to 1.34g(3.7mmol) 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-add 1.0ml(11.1mmol in the 25ml dichloromethane solution of 4-fluorobenzoic acid) oxalyl chloride, gas evolution is arranged.When effusion stops, adding till 1 DMF and stirred solution stop to gas evolution.Solution for vacuum is stripped to dried.Residuum is dissolved among the 5mlTHF and under 0 ℃, in 5 minutes it is added in the 10ml40% aqueous methylamine solution.Stirring at room reaction mixture 30 minutes.In solution impouring 150ml cold water, filter, and dry air.Solid obtains 0.95g(69% with methylcyclohexane/re-crystallizing in ethyl acetate) 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-4-fluoro-N-methyl-benzamide, be white solid, mp187 ℃.
Ultimate analysis C
13H
12Cl
2F
1N
3O
3S
1:
Calculated value: C, 41.07; H, 3.18; N, 11.05.
Measured value: C, 41.12; H, 3.13; N, 11.03.
Embodiment 25
Present embodiment has illustrated 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl) the 1H-pyrazole-3-yl)-preparation of 4-fluorobenzene mercaptan, be the concrete operations embodiment of method XI.
With 9.3g(0.022mol) 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-4-fluorobenzene SULPHURYL CHLORIDE and 29g(0.44mol) the 125ml glacial acetic acid pulpous state liquid of zinc powder stirred 4 hours at 90 ℃.Cooling pulpous state liquid also passes through Celite
Filter, in filtrate impouring 1 premium on currency and filter pulpous state liquid, dry air.Solid ethanol/water recrystallization obtains 5.8g(74%) 2-chloro-5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-4-fluorobenzene mercaptan, be white solid, mp111 ℃.
Ultimate analysis C
11H
9Cl
2F
1N
2O
2S
2:
Calculated value: C, 37.19; H, 2.55; N, 7.86; S, 18.05.
Measured value: C, 37.29; H, 2.44; N, 7.86; S, 17.95.
Embodiment 26
Present embodiment has illustrated 4-chloro-3-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-1-methyl-5-(ethylsulfonyl)-preparation of 1H-pyrazoles, and as the concrete operations embodiment of method XII.
All appts is used the flame drying under nitrogen atmosphere.Under-78 ℃; to 4-chloro-3-(4-chloro-2-fluoro-5-p-methoxy-phenyl)-1-methyl-5-(methylsulfonyl)-1H-pyrazoles (1.25g; 3.5mmol) the 50ml anhydrous tetrahydrofuran solution in add 1M n-butyllithium solution (3.5ml; 3.5mmol), and allowable temperature does not rise and above-60 ℃.Be reflected at-78 ℃ and stirred 30 minutes, in reaction, add then methyl iodide (0.49g, 3.5mmol).Reactant is heated to room temperature, then in the impouring ice and use ethyl acetate extraction.Organism salt solution washed twice is used anhydrous magnesium sulfate drying, and vacuum concentration.Residuum is through chromatogram purification, adopts 1: 1 hexane and ethyl acetate solvent system, obtains the 0.5g(39% productive rate) yellow solid, mp65 ℃.
Ultimate analysis C
13H
13N
2O
3S
1Cl
2:
Calculated value: C, 42.52; H, 3.57; N, 7.63.
Measured value: C, 42.53; H, 3.80; N, 7.71.
Embodiment 27
Present embodiment has illustrated 7-[4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl]-6-fluoro-2H-1, the preparation of 4-benzothiazine-4(3H)-ketone, and as the concrete operations embodiment of method X III.
With ((5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-4-fluoro-2-nitrophenyl) sulfo-) ethyl acetate (3.0g; 6.6mmol) glacial acetic acid (150ml) solution be heated to 80 ℃; and once add iron (1.5g, 0.0268mol).Solution was 80 ℃-100 ℃ heating 1 hour, and Celete is passed through in cooling then
Filter and wash with water to solid disengaging solution.Leach solid and obtain 1.7g(68%) compound described in first section of the present embodiment, be white solid, mp245 ℃.
1HNMR（CDCl
3）ppm：7.28（d，J＝7.2，1H），6.79（d，J＝10.8，1H），4.1（S，3H），3.27（S，2H），3.22（S，3H）。
Ultimate analysis C
13H
11Cl
1F
1N
3O
3S
1:
Calculated value: C, 41.55; H, 2.95; N, 11.18.
Measured value: C, 41.72; H, 3.09; N, 10.81.
Table 3 and 4 is listed with the prepared examples of compounds of arbitrary combination as the illustrational method II of embodiment 1-27-X III and/or these methods.
The preemergence herbicide test
As previously mentioned, find that The compounds of this invention is effective especially as weedicide.
The preemergence herbicide activity test is carried out as follows:
Table soil is positioned in the shallow basin of aluminium, and to be compacted to it apart from the degree of depth of basin upper end be 0.95 to 1.27cm.The nutrition propagule of the seed of several unifacial leaves of predetermined number and dicotyledonous yearly plant kind and/or multiple perennial plant kind respectively be placed on soil above.The activeconstituents of dose known amounts is dissolved in or is suspended in organic solvent, in acetone or water, directly be applied to seed bed then, with the untreated table soil of one deck basin is filled up again and pave as carrier.After handling, shallow basin is moved on the chamber planting platform, in order to reach the humidity of suitable germinating growth, water from below when needing.
Observe shallow basin and write down result's (% inhibiting rate) when about 10/14 day (being generally 11 days) in sowing and after handling.
Following table 5 concluded The compounds of this invention to the bud of multiple weeds before the weeding activity test-results.The weeding rate of listing in the table 5 is the percent inhibition of each plant variety.
Used the plant variety that is considered to weeds usually in battery of tests, data are listed in table 5, and these plant varieties mark by following symbol with the letter topic head of top line.
The Yens-tiger nuts
The Anbg-annual meadow grass
Sejg-stone thatch Chinese sorghum (Seedling johnsongrass)
The Dobr-downy brome
The Bygr-barnyard grass
The Mogl-morning glory
The Cobu-Radix Agrimoniae
The Vele-piemarker
The Inmu-leaf mustard
Wibw-fine hair Polygonum
The symbol that in following table, writes down " C " expression 100% control, this plant has been planted in symbol " N " expression, but owing to this or the sort of reason does not obtain data.
Table 5
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
22 1.12 80 c c c c c 70 c c c
23 1.12 30 20 80 30 20 c 80 90 90 c
24 11.21 70 c 90 70 c 90 70 c c c
25 11.21 0 80 80 70 80 70 30 c c 90
26 11.21 0 0 0 0 0 0 0 80 10 0
27 11.21 0 0 50 20 20 30 40 90 70 10
28 11.21 c c 70 80 c c c c c c
29 11.21 20 c 80 40 c c 0 c c 90
30 1.12 80 40 40 10 80 c c c c c
31 11.21 40 10 70 0 c 80 80 80 80 80
32 11.21 c c c c c c c c c c
33 11.21 90 c 90 c c c 70 c c c
34 11.21 90 c 90 60 c c 70 c c c
35 11.21 90 c c 50 c c 60 c c c
36 11.21 30 30 60 c 90 60 60 c c c
37 11.21 60 80 90 30 c c c c c c
38 11.21 80 80 80 50 c 90 70 90 c c
39 11.21 90 c 90 80 c c c c c c
40 1.12 70 c 70 40 80 c 60 c c 90
41 1.12 70 50 30 10 80 c 20 c c c
42 11.21 80 80 90 80 c c c c c c
43 1.12 70 c c 50 90 c c c c c
Table 5(is continuous)
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
44 11.21 90 c c c c c 90 c c c
45 11.21 c c c c c c c c c c
46 1.12 0 0 30 10 0 10 20 70 70 c
47 1.12 0 60 80 10 70 80 10 90 c c
48 1.12 0 30 60 20 c 40 20 80 90 c
49 1.12 0 90 90 10 90 90 30 c c c
50 11.21 20 80 70 60 90 c 20 c 90 c
51 11.21 50 c c 80 c 80 c 90 c c
52 1.12 10 c c 90 90 80 60 c c c
53 1.12 0 10 0 90 40 90 50 c c 60
54 1.12 40 10 30 20 0 70 30 c 90 90
55 1.12 10 0 0 20 20 c 90 90 c c
56 1.12 10 90 80 60 70 90 70 c c c
57 1.12 10 0 0 0 0 30 20 70 80 70
58 1.12 70 40 70 10 c 90 c c c c
59 11.21 50 c c 80 c 90 90 c c c
60 1.12 30 70 c 90 80 60 40 c 70 c
61 1.12 50 90 60 50 90 c 40 c c c
62 1.12 0 c 80 70 80 90 c 80 c 80
63 1.12 40 50 90 90 c 80 c c c c
64 1.12 30 20 30 80 c 70 c 90 c 90
65 1.12 40 80 70 50 c c 60 c c c
Table 5(is continuous)
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
66 1.12 60 c 90 40 c c 70 c c c
67 1.12 0 c 70 80 c c 80 c c c
68 ＊ 1.12 20 90 60 20 90 90 70 c c 90
69 1.12 60 c 90 50 90 c 30 c c c
70 1.12 30 c 90 40 c c 30 c c c
71 1.12 30 c 90 40 c 80 30 c c 90
72 1.12 60 20 60 20 80 c c 90 90 90
73 1.12 50 10 60 30 50 90 80 80 90 80
＃ 1.12 40 0 80 10 20 90 60 80 90 80
74 1.12 70 20 70 0 80 c c c c c
75 1.12 50 0 70 20 80 c 40 c 90 c
76 1.12 60 20 30 20 70 c 90 90 90 80
77 1.12 20 0 20 20 80 c 70 c 80 80
78 1.12 60 c 90 50 c c c c c c
79 1.12 90 c 70 20 90 c c c c c
80 1.12 60 10 70 20 20 c 60 90 90 90
81 1.12 60 c c 90 c 90 80 c c c
82 1.12 50 50 80 20 90 c 90 c c 90
83 1.12 70 c c c c c 60 c c c
84 1.12 0 80 70 80 80 c 80 c c c
85 11.21 90 90 90 90 90 90 c c c c
86 1.12 0 20 30 20 20 40 20 40 80 90
Table 5(is continuous)
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
87 1.12 0 70 80 80 60 c 80 c c c
88 1.12 20 40 80 80 60 c 80 c c c
89 1.12 0 20 40 30 80 80 80 c c c
90 1.12 0 0 0 20 30 60 30 c c c
91 1.12 20 10 10 50 70 60 60 c c c
92 1.12 0 80 40 60 50 c 60 c c 90
93 11.21 0 10 0 10 50 20 0 80 80 10
94 11.21 60 c c 70 c 90 30 c c c
95 11.21 70 c c 70 c c 80 c c c
96 11.21 70 c c c c c 20 c c c
97 11.21 20 20 40 20 80 40 20 c c 80
98 11.21 0 0 20 0 0 0 0 0 0 30
99 11.21 0 0 0 0 0 0 0 20 0 0
100 11.21 0 0 0 0 0 0 0 0 0 0
101 11.21 0 0 70 0 80 60 20 50 70 0
102 11.21 40 30 60 30 80 50 0 60 c 90
103 11.21 20 80 80 20 80 90 70 90 80 90
104 11.21 40 c 80 80 90 70 80 c c c
105 11.21 40 80 90 70 90 80 60 c c 70
106 11.21 0 60 70 30 60 40 70 c 90 90
107 11.21 40 90 70 60 c 70 c c c 50
108 11.21 30 90 90 70 80 90 80 c c c
Table 5(is continuous)
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
109 11.21 70 c c 60 90 80 90 c c c
110 11.21 80 c 90 80 90 90 90 c c 80
111 11.21 40 c 70 70 c 20 c c c 70
112 11.21 80 c c 70 90 c 70 c c c
113 1.12 60 80 90 50 c 30 60 90 c 90
114 11.21 0 0 0 20 20 70 20 30 30 20
115 11.21 c 40 90 80 c c c c c c
116 11.21 90 0 80 20 60 90 60 c c c
117 11.21 70 80 90 70 c 70 90 c c c
118 11.21 0 0 0 0 0 0 0 80 20 10
119 11.21 0 0 0 0 0 0 0 30 20 10
120 11.21 0 0 0 0 0 0 0 0 30 20
121 11.21 0 0 0 0 0 0 0 20 0 0
122 11.21 0 0 0 0 0 0 0 10 10 20
123 11.21 40 90 90 20 90 70 40 80 90 90
124 11.21 50 20 40 20 70 70 20 90 c 50
125 11.21 0 0 0 0 0 20 0 70 40 40
126 11.21 30 60 40 20 80 70 20 c 90 80
127 11.21 80 c c c c c c c c c
128 1.12 80 c 90 70 90 90 c c c c
129 11.21 40 70 60 90 80 80 c c c c
130 1.12 40 c 80 80 90 c 60 c c c
Table 5(is continuous)
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
131 1.12 80 20 80 20 70 c 30 c 90 c
132 1.12 0 30 80 c 80 80 30 c c c
133 1.12 10 20 90 40 10 80 30 c 80 c
134 1.12 c c 90 90 c 90 c c c c
135 1.12 c 10 80 10 c c 60 c c c
136 1.12 10 90 90 40 c c 20 c c c
137 11.21 90 c c c c c c c c c
138 11.21 0 0 0 0 0 0 0 80 20 70
139 11.21 20 90 80 90 80 90 90 c c c
140 11.21 80 60 c 20 c c c c c c
141 1.21 30 90 70 60 80 80 20 c 90 90
142 11.21 60 c 90 20 90 90 60 c c c
143 1.12 0 40 20 10 20 20 80 30 80 70
144 11.21 0 20 0 20 0 0 0 20 20 20
145 11.21 0 10 10 20 30 20 30 30 20 40
146 11.21 60 c c c c 80 30 c c c
147 11.21 60 c 90 70 c 80 20 c c 90
148 11.21 80 c c c c 90 50 c c c
149 11.21 0 0 0 0 0 50 20 70 60 80
150 11.21 0 0 0 0 0 0 0 0 0 0
151 11.21 30 90 90 30 90 c 80 c c c
152 11.21 0 0 0 0 0 0 0 0 0 0
Table 5(is continuous)
Test before the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
153 1.21 30 60 c 70 90 80 40 c c c
154 1.12 70 c 80 80 90 c c c c c
155 1.12 80 c c 60 c c c c c c
156 1.12 0 c 90 30 90 90 90 c c 80
157 1.12 70 c 90 c c c c c c c
158 1.12 10 10 80 40 30 50 40 80 20 30
159 11.21 0 0 0 0 0 0 0 0 0 0
＊Wibw-THIN
^ is excessively dampinged off
# is about, and 4 weeks observed
Weeding test behind the bud
Weeding activity is by the greenhouse test explanation of being undertaken by following mode behind the bud of compounds more of the present invention.To show soil and be placed in the foraminous aluminium shallow basin of bottom, and to be compacted to apart from the basin top degree of depth be 0.95 to 1.27cm.On soil, respectively place all kinds of unifacial leaves and the seed of dicotyledonous yearly plant kind and/or the nutrition propagule of perennial plant kind of predetermined number, and be pressed into soil surface, cover seed and/or nutrition propagule and pave with soil.Then basin is placed on the chamber planting platform, when needing from below water.Treat that plant-growth arrives required period (two to three weeks), every basin moved on in the spray chamber one by one by atomizer spray, with the given ratio of using, at spray pressure 170.3kpa(10psig) under operate.Spray solution is the emulsifier mixture of some amount, so that form the spray solution or the suspension of the emulsifying agent that contains 0.4% volume ratio.The selected chemical substance that contains capacity in spray solution or the suspension is obtaining using ratio with the corresponding activeconstituents of table 2, and solutions employed or suspension total amount equal the 1870L/ha(200 gallon/acre).Basin sent back in the greenhouse and by former mode waters, after spray approximately 10-14 days (being generally 11 days) observe with control group relatively to the injury situation of plant, and in some cases, 24-28 days (common 25 days) are observed again after spraying.Weeding activity is the percent inhibition of each plant variety behind the bud that table 6 is listed.
Table 6
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha e g g r r l u e u w
22 1.12 40 40 30 50 30 c c c 80 80
23 1.12 50 20 40 40 80 c c c 60 c
24 11.21 40 60 80 30 90 80 70 c 90 c
25
11.21 10 0 10 0 0 20 20 30 40 90
26 11.21 0 0 10 0 0 20 20 20 30 0
27 11.21 0 0 0 0 10 30 10 90 50 70
28 11.21 20 10 10 0 10 80 c c 90 c
29 11.21 20 10 60 10 0 20 20 c 70 60
30 1.12 0 10 30 20 30 90 90 90 80 80
31
11.21 0 20 20 0 20 80 80 c 50 60
32 11.21 40 90 90 c 90 c 90 c 90 c
33 11.21 30 90 c c c 90 c c c c
34 11.21 20 40 70 10 70 80 80 c 90 80
35 11.21 30 10 70 0 c c 80 c 80 70
36
11.21 20 20 50 30 40 60 60 c 70 c
37 11.21 30 80 90 90 c c c c c c
38
11.21 20 60 70 0 70 c 60 c 60 60
39 11.21 30 80 80 20 90 c 50 c 90 80
40 1.12 40 90 90 c c 90 c c 90 90
41 1.12 10 10 70 80 c c 60 c 90 70
42 11.21 60 90 90 40 80 c c c c c
43 1.12 20 0 40 30 30 90 90 c 80 70
Table 6(is continuous)
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
44 11.21 40 c c c c c c c c c
45 11.21 30 90 c 90 c c c c c c
46 1.12 20 0 0 0 0 30 30 30 30 60
47 1.12 20 0 20 20 0 30 30 50 40 80
48 1.12 10 20 20 20 20 c 60 c 40 80
49
1.12 0 10 0 0 0 40 30 50 40 60
50 11.21 20 30 90 50 50 70 60 90 c c
51
11.21 0 20 40 20 50 90 c c 80 c
52 1.12 20 40 20 20 40 90 60 c 70 c
53 1.12 20 20 80 50 90 90 c c 80 90
54 1.12 0 20 40 20 10 30 40 70 60 60
55 1.12 30 10 40 20 80 c c c 70 c
56
1.12 20 50 20 20 0 90 90 c 70 90
57 1.12 0 0 0 0 0 20 20 60 50 80
58
1.12 20 10 20 0 30 c 90 c 70 c
59
11.21 20 60 80 20 80 c 90 90 80 c
60 1.12 20 20 60 20 60 c c c 50 80
61 1.12 30 60 90 c c 60 c c 80 90
62 1.12 20 50 80 50 50 50 80 90 70 80
63 1.12 30 80 c c c c c 90 90 c
64 1.12 30 90 c c 90 c c c c c
65 1.12 30 60 80 90 90 c c 90 c 90
Table 6(is continuous)
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
66 1.12 30 60 80 50 40 c 80 c 50 c
67 1.12 30 70 70 80 70 90 90 c c c
68 1.12 30 40 90 50 30 60 60 90 60 40
69 1.12 40 50 50 90 70 c c c 70 c
70 1.12 20 30 20 20 20 c c c 80 70
71 1.12 20 90 90 90 80 c c 90 60 c
72 1.12 10 0 50 20 50 90 80 90 20 60
73 1.12 30 10 80 20 c 80 90 c 50 c
74 1.12 20 20 70 40 60 c c c 60 c
75 1.12 50 0 30 20 40 c c c 50 c
76 1.12 20 20 80 50 70 c c 90 60 80
77 1.12 20 20 60 30 60 c c 90 50 c
78 1.12 20 30 30 50 30 c 80 90 60 70
79 1.12 20 0 70 20 0 c 90 90 60 c
80 1.12 30 10 70 20 60 c c 90 80 90
81 1.12 10 c c c c 90 c c c c
82 1.12 20 20 30 0 0 80 80 c 40 30
83 1.12 10 90 c c c c c 90 90 c
84 1.12 20 70 c 90 90 90 70 c 80 c
85 11.21 30 60 90 60 90 c 90 90 90 c
86 1.12 10 30 20 30 20 60 50 c 50 90
Table 6(is continuous)
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
87 1.12 10 40 80 c c c c c 90 90
88 1.12 20 70 80 c c c c c c 80
89 1.12 10 50 60 70 40 90 90 90 90 80
90 1.12 0 20 80 90 90 90 80 c 80 80
91 1.12 10 40 90 90 90 80 c 90 90 80
92 1.12 40 70 70 80 30 c c c 90 40
93 11.21 0 0 20 10 70 80 80 c 90 70
94 11.21 10 20 0 0 0 20 80 70 60 40
95 11.21 10 20 20 0 0 20 30 c 90 c
96 11.21 10 20 90 50 90 60 30 c 40 c
97 11.21 0 0 0 0 0 20 30 60 30 80
98 11.21 0 0 0 0 0 10 10 0 0 0
99 11.21 0 0 0 0 0 0 0 30 0 0
100 11.21 0 0 20 0 20 0 0 30 10 20
101 11.21 0 0 20 0 0 30 20 20 0 40
102 11.21 0 10 20 10 30 20 10 30 20 60
103 11.21 0 0 0 0 0 0 0 0 0 60
+ 11.21 0 0 20 0 30 30 50 50 30 60
104 11.21 10 20 40 0 40 50 60 80 70 c
105 11.21 20 60 80 30 30 80 70 c 80 c
106 11.21 0 0 0 0 0 40 40 50 40 80
107 11.21 20 50 80 50 60 c c c c c
Table 6(is continuous)
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
108 11.21 30 30 60 20 30 60 50 90 50 c
109 11.21 30 30 40 20 40 30 30 90 50 c
110 11.21 30 70 80 40 50 50 70 c 70 c
111 11.21 0 40 20 0 10 20 10 70 80 50
112 11.21 20 60 90 40 50 40 70 c 80 c
113 1.12 0 0 10 0 10 10 10 20 0 90
114 11.21 0 0 0 0 0 0 30 20 0 40
115 11.21 30 30 c 90 90 90 c c c c
116 11.21 20 20 60 30 50 80 70 c 50 60
117
11.21 10 50 50 40 80 60 50 c 90 c
118 11.21 0 0 0 0 0 20 0 20 10 0
119 11.21 10 0 0 0 0 0 0 0 0 0
120 11.21 0 0 0 0 0 0 0 10 0 0
121 11.21 0 0 0 0 0 20 20 0 0 0
122 11.21 0 0 0 0 0 20 0 20 0 20
123 11.21 0 20 0 0 0 20 50 60 20 c
124 11.21 0 0 0 0 0 0 0 30 20 20
125 11.21 0 0 0 0 0 0 0 20 0 0
126 11.21 0 0 0 0 0 20 20 40 20 50
127 11.21 10 90 90 70 c c 70 c c c
128 1.12 10 50 40 80 80 80 80 80 60 c
129 11.21 10 30 30 0 30 80 50 c 80 c
Table 6(is continuous)
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
130 1.12 30 60 40 50 20 c c c c c
131 1.12 40 20 60 20 70 c 90 c 40 80
132 1.12 30 30 40 80 80 c c c 80 80
133 1.12 10 40 40 80 90 90 90 c 40 40
134 1.12 0 90 80 c c c c c 80 50
135 1.12 20 10 80 0 60 c 80 c 50 50
136 1.12 10 20 60 30 20 80 80 c 90 90
137 11.21 20 c c c c c 90 c c c
138 11.21 0 0 20 0 0 40 30 40 20 c
139 11.21 10 30 80 30 20 50 40 c c c
140 11.21 20 10 80 10 70 60 50 c 70 70
141 1.12 0 90 90 80 70 80 70 c 70 70
142 11.21 10 20 80 20 10 40 30 80 30 70
143 1.12 20 90 90 c 70 c c c 90 50
144 11.21 0 20 0 20 0 20 20 30 20 50
145
11.21 10 0 0 0 10 20 20 40 40 20
146
11.21 10 70 80 90 90 60 60 c 80 c
147 11.21 0 60 80 30 80 80 70 c 90 c
148 11.21 10 40 40 0 20 20 30 c 90 c
149
11.21 0 0 0 0 0 10 10 10 0 40
150
11.21 0 0 0 0 0 20 0 0 0 20
151 11.21 10 0 0 0 0 60 60 80 60 c
Table 6(is continuous)
Test behind the bud
% plant inhibiting rate
Use W than Y A S D B M C V I
e n e o y o o e n i
Compound n b j b g g b l m b
Numbering kg/ha s g g r r l u e u w
152 11.21 0 0 0 0 0 0 0 0 0 0
153 11.21 10 10 10 0 20 40 30 80 80 c
154 1.12 20 c 80 80 70 70 80 c c 80
155 1.12 10 90 80 70 90 70 c c 90 30
156 1.12 10 80 c 30 50 90 40 c 90 70
157 1.12 20 90 90 90 90 c c c 90 80
158 1.12 10 70 70 60 40 c c c 70 50
159 11.21 0 0 0 0 0 20 10 10 0 0
The Agrimony response of difference
+ revision test
Herbicidal composition of the present invention comprises using needs dense dose of dilution before, wherein can contain the auxiliary agent of at least a active ingredient and liquid or solid form.With the mixed composition that gets of activeconstituents and the auxiliary agent that includes thinner, filler, carrier and conditioning agent, the composition that obtains can be the form of granulous granular solids in small, broken bits, granula, pill, solution, dispersion agent or emulsion.Therefore, be sure of activeconstituents can with auxiliary agent, grain for example in small, broken bits solid, organic liquid, water, wetting agent, dispersion agent, emulsifying agent or its any suitable combination are together used.
Known suitable wetting agent comprises alkylbenzene and sulfonated alkyl naphathalene, Sulfated Fatty Alcohol(C12-C14 and C12-C18), amine or acid amides, the long-chain acid esters of different Sulfothiorine (sodiumisothionate), sulfo-succsinic acid sodium ester, sulfation or sulfonated fatty acid ester, sulfonated petro-leum, sulfonated vegetable oil, two uncle's acetylenic glycol classes (ditertiary acetylenic glycols), the polyoxyethylene deriv of alkylphenol (especially isooctyl phenol and nonylphenol), and the polyoxyethylene deriv of a high-grade aliphatic ester of hexitan (as anhydro sorbitol).Preferred dispersing agent is methylcellulose gum, polyvinyl alcohol, sodium lignosulfonate, poly-sulfonated alkyl naphathalene, sodium naphthalene sulfonate, polymethylene bis napsylate.Wettable powder is the water dispersible composition that contains one or more activeconstituentss, inert solid fillers and one or more wetting agents and dispersion agent.The synthesizing inorganic thing that inert solid fillers is generally natural clay, diatomaceous natural mineral matter and is derived and obtained by silicon-dioxide or its analogue.The example of these fillers comprises kaolin, U.S.'s atlapulgite and synthetic magnesium silicate.Wettable powder composition of the present invention contains the active ingredient of about 0.5 to 60 part (being preferably 5-20 part) usually, the wetting agent of about 0.25-25 part (being preferably 1-15 part), dispersion agent of about 0.25-25 part (being preferably 1.0-15 part) and 5 inert solid fillers to about 95 parts (being preferably 5-50 part), all umbers are all with the total weight of composition.If desired, wherein about 0.1 to 2.0 part solid, inert filler can be by sanitas or foam reducing composition, or its two replace.
Other preparation comprises and is stated from pulvis enriching agent suitable filler, that contain 0.1 to 60% weight ratio activeconstituents, can be with this Dilution for powder in about 0.1-10% weight ratio concentration range when using.
The preparation of aqueous suspension agent or emulsion can be stirred to evenly by non-aqueous solution and the water with water-insoluble activeconstituents and emulsifying agent, and homogenizing is to obtain particulate stable emulsion very in small, broken bits then.The characteristics of formed dense suspension aqua are that very tiny granularity is arranged, thereby when dilution and spraying, can cover very evenly.The suitable concn of these preparations is preferably the active ingredient of 5-50% weight ratio for containing the 0.1-60% that has an appointment, and its upper limit is by the solubility limit decision of active ingredient in solvent.Enriching agent is generally active ingredient with solution and the tensio-active agent of tensio-active agent in water unmixing or portion water immiscible solvent.The suitable solvent of active ingredient of the present invention comprises dimethyl formamide, methyl-sulphoxide, N-Methyl pyrrolidone, hydrocarbon and water unmixing ether, ester or ketone.And other high concentration liquid enriching agent can for example be diluted to spray concentration with kerosene and make then by active ingredient is dissolved in the solvent.
Enriching agent composition described here generally contains the active ingredient of have an appointment 0.1 to 95 part (being preferably 5-60 part), about 0.25 to 50 part of (being preferably 1-25 part) tensio-active agent, and the solvent that contains 5 to 94 parts when needing.All umbers with the gross weight of missible oil be benchmark by weight.
Granula is the physically stable particulate composition that contains the active ingredient on the matrix that is adsorbed in or is dispersed in inert, particle extender in small, broken bits.In order to help active ingredient from granular filler, to ooze out, can use above listed tensio-active agent in the composition, available particulate inorganic filler examples of types has natural clay, pyrophyllite, illite and vermiculite.Preferred extender is filler porous, adsorptivity, moulding such as moulding and the granular U.S. atlapulgite through screening or the particulate state vermiculite of expanded by heating, and clay in small, broken bits such as kaolin, hydration U.S. atlapulgite or wilkinite, these fillers form granulated herbicide with activeconstituents through spraying or mixing.
The clay of per 100 parts by weight contains the activeconstituents of about 0.1 to 30 parts by weight and the particulate of per 100 parts of parts by weight contains 0 tensio-active agent to about 5 parts by weight in the granule composition of the present invention.
The present composition also can contain other additive, for example, and fertilizer, other weedicide, other sterilant, protective agent and as the analogue of auxiliary agent, or the arbitrary combination of above-mentioned auxiliary agent.Can comprise with the chemical that activeconstituents of the present invention is used in combination, the for example ether (heterophenylethers) of triazine, ureas, sulfonylurea, amino formate, ethanamide, monoacetylaniline class, uracil, acetate or phenol derivatives, sulfur hydroxy carbamate, triazole, benzoic acid derivative, nitrile, different phenyl, nitrophenyl ether, phenyl ether, pyridine etc., for example
Heterocyclic nitrogen/sulfur derivatives
2-chloro-4-ethylamino-6-isopropylamino-S-triazine
2-chloro-4,6-two (isopropylamino)-S-triazine
2-chloro-4,6-two (ethylamino)-S-triazine
3-sec.-propyl-1H-2,1, the 3-benzothiadiazine-4-(3H)-and ketone 2, the 2-dioxide
3-amino-1,2, the 4-triazole
6,7-dihydro dipyridyl also (1,2-:2 ', 1 '-C)-pyrazine salt
5-bromo-3-sec.-propyl-6-6-Methyl Uracil
1,1 '-dimethyl-4,4 '-dipyridyl
2-(4-sec.-propyl-4-methyl-5-oxo-2-tetrahydroglyoxaline-2-yl)-the 3-quinoline carboxylic acid
2-(4-sec.-propyl-4-methyl-5-oxo-2-tetrahydroglyoxaline-2-yl) nicotinic acid isopropyl amine salt
6-(4-sec.-propyl-4-methyl-5-oxo-2-tetrahydroglyoxaline-2-yl)-meta-toluic acid methyl esters and 2-(4-sec.-propyl-4-methyl-5-oxo-2-tetrahydroglyoxaline-2-yl)-right-toluic acid methyl esters
The 5-(trifluoromethyl)-4-chloro-3-(3 '-[1-ethoxycarbonyl]-oxyethyl group-4 '-nitro-phenoxy)-the 1-methylpyrazole;
The 5-(trifluoromethyl)-4-chloro-3-(3 '-methoxyl group-4 '-nitro-phenoxy)-the 1-methylpyrazole;
The 5-(trifluoromethyl)-4-chloro-3-(3 '-[1-butoxy carbonyl] oxyethyl group-4 '-nitro-phenoxy)-4-methylpyrazole;
The 5-(trifluoromethyl)-4-chloro-3-(3 '-first sulphonamide carbonyl propoxy--4 '-nitro-phenoxy)-4-methylpyrazole;
The 5-(trifluoromethyl)-4-chloro-3-(3 '-third oxygen carbonyl methyl oximido-4 '-nitro-phenoxy)-the 1-methylpyrazole;
(+)-2-[4-[[5-(trifluoromethyl)-and the 2-pyridyl] oxygen] phenoxy group]-propionic acid (9CI);
S, S-dimethyl-2-(difluoromethyl)-4-isobutyl--6-trifluoromethyl-3,5-pyridine dithiocarboxylic esters;
The 2-(difluoromethyl)-and 5-(4,5-dihydro-2-thiazolyl)-the 4-(2-methyl-propyl)-the 6-(trifluoromethyl)-3-pyridine carboxylic acid methyl esters;
The 2-(difluoromethyl)-the 4-(2-methyl-propyl)-the 6-(trifluoromethyl)-3,5-pyridine dicarboxylic acid dimethyl ester;
4-(cyclopropyl methyl)-the 2-(difluoromethyl)-the 6-(trifluoromethyl)-3,5-pyridine dithionic acid-S, S-dimethyl ester;
N-(diethoxy phosphinyl)-S-methyl-S-phenyl-sulfime.
Ureas and sulfonylurea
The N-(4-chlorophenoxy) phenyl-N, the N-dimethyl urea
N, N-dimethyl-N '-(3-chloro-4-aminomethyl phenyl) urea
3-(3, the 4-dichlorophenyl)-1, the 1-dimethyl urea
1,3-dimethyl-3-(2-benzothiazolyl) urea
3-(is right-chloro-phenyl-) and-1, the 1-dimethyl urea
1-butyl-3-(3, the 4-dichlorophenyl)-1-methyl urea
2-chloro-N-[(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) amino-carbonyl]-benzsulfamide
2-(((((4,6-dimethyl-2-pyrimidyl) amino) carbonyl) amino) alkylsulfonyl)-methyl benzoate
1-[methyl 2-(((((4,6-dimethyl-2-pyrimidyl) amino) carbonyl)-amino) alkylsulfonyl)] ethyl benzoate
2((4,6-dimethoxypyridin-2-yl) aminocarboxyl) the aminosulfonyl ylmethyl) methyl benzoate
2-(((((4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) amino) carbonyl) amino) alkylsulfonyl) methyl benzoate
N-[3-(N, the N-formyl-dimethylamino)-2-pyridine-2-yl]-alkylsulfonyl-N '-(4,6-dimethoxypyridin-2-yl) urea
The N-[(3-ethylsulfonyl)-2-pyridine-2-yl]-alkylsulfonyl-N '-(4,6-dimethoxy-pyrimidine-2-base) urea
N-(2-methoxycarbonyl phenyl alkylsulfonyl)-N '-(4,6-pair-the difluoro-methoxy pyrimidine-2-base) urea
Carbamate/thiol-carbamate
Diethyldithiocar bamic acid 2-chlorallyl ester
N, N-diethyl sulfide hydroxylamino formic acid S-(4-benzyl chloride base) ester
The N-(3-chloro-phenyl-) carbamic acid isopropyl ester
N, N-di-isopropyl thiol carboxylamine S-2,3-dichloro allyl ester
S-N, N-dipropyl sulphur hydroxybutyl carbamate
N, N-dipropyl sulphur hydroxylamino formic acid S-propyl diester
S-2,3,3-three chlorallyls-N, N-di-isopropyl thiol-carbamate
Ethanamide/monoacetylaniline/aniline/acid amides
2-chloro-N, N-diallyl ethanamide
N, N-dimethyl-2,2-phenylbenzene ethanamide
N-(2,4-thioxene-3-yl)-N-(1-methoxy propyl-2-yl)-the 2-chlor(o)acetamide
N-(1H-pyrazol-1-yl methyl-N-(2,4-thioxene-3-yl)-the 2-chlor(o)acetamide
N-(1-pyrazol-1-yl methyl)-and N-(4,6-dimethoxypyridin-5-yl)-the 2-chlor(o)acetamide
N-(2,4-dimethyl-5-[[[(trifluoromethyl) alkylsulfonyl] amino]-phenyl] ethanamide
N-sec.-propyl-2-chloro-monoacetylaniline
N-sec.-propyl-1-(3,5,5-trimethyl cyclohexene-1-yl)-the 2-chlor(o)acetamide
2 ', 6 '-diethyl-N-(butoxymethyl)-2-chloro-monoacetylaniline
2 ', 6 '-diethyl-N-(2-just-the propoxy-ethyl)-2-chloro-monoacetylaniline
2 ', 6 '-dimethyl-N-(1-pyrazol-1-yl methyl)-2-chloro-monoacetylaniline
2 ', 6 '-diethyl-N-methoxymethyl-2-chloro-monoacetylaniline
2 '-methyl-6 '-ethyl-N-(2-methoxy propyl-2-yl)-2-chloro-monoacetylaniline
2 '-methyl-6 '-ethyl-N-(ethoxyl methyl)-2-chloro-monoacetylaniline
α, α, α-three fluoro-2,6-dinitrobenzene-N, N-dipropyl-right-N-Tolylamine
N-(1, the 1-alkynyl dimethyl)-3, the 5-dichloro-benzamide
Acid/ester/alcohol
2,2 dichloropropionic acid
2-methyl-4-chlorophenoxyacetic acid
The 2,4 dichloro benzene ethoxyacetic acid
Methyl-2-[4-(2, the 4-dichlorophenoxy) phenoxy group] propionic ester
3-amino-2, the 5-dichlorobenzoic acid
2-methoxyl group-3, the 6-dichlorobenzoic acid
2,3,6-trichlorophenyl acetate
N-1-naphthyl phthalamic acid
5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoic acid sodium
4,6-dinitrobenzene-neighbour-sec-butyl phenol
The N-((phosphonomethyl)) glycine and salt thereof
(R)-the 2-[4-[(5-(trifluoromethyl)-the 2-pyridyl) the oxygen base] phenoxy group] butyl propionate
Ether
2,4 dichloro phenol-4-nitrophenyl ether
2-chloro-δ, δ, δ-three fluoro-is right-tolyl-3-oxyethyl group-4-itrodiphenyl ethers
5-(2-chloro-4-4-trifluoromethylphenopendant)-N-methylsulfonyl-2-nitrobenzamide
1 '-(ethoxycarbonyl) ethyl 5-[2-chloro-4-(trifluoromethyl) phenoxy group]-2-nitrobenzoyl acid esters
Other
2, the 6-dichloro-benzonitrile
Monomethylarsinic acid one sodium (monosodium acid methanearsonate)
Tonarsin
The 2-(2-chloro-phenyl-) methyl-4,4-dimethyl-3-isoxazole alkyl ketone
7-oxabicyclo (2,2,1) heptane, 1-methyl-4-(1-methylethyl)-2-(2-aminomethyl phenyl methoxyl group)-, outer-glyphosate and salt thereof.
Can merge the fertilizer that uses with active ingredient and comprise, for example, ammonium nitrate, urea, salt of wormwood and calcium superphosphate.Other useful annexation comprises plant organic tissue the take root material such as the compost of growth needs, fertilizer, and vegetable mould, husky or the like.
Above-mentioned herbicide formulations type can be illustrated by following several illustrative embodiment.
I. missible oil
Weight percent
A. compound 22 4.0
The free acid of compound organophosphate or
The hydrophobic alkali of aromatic series or aliphatics
(as, GAFAC RE-610, GAF register of company trade mark 3.5
Polyoxyethylene/polyoxypropylene with
The segmented copolymer of butanols (as, Tergitol
XH, Union Carbide register of company trade mark 1.5
Dimethylbenzene 5.34
Mono chloro benzene 85.66
100.00
B. compound 36 3.0
The free acid of compound organophosphate or fragrance
The hydrophobic alkali of family or aliphatics (as,
GAFAC RE-610） 4.0
Polyoxyethylene/polyoxypropylene and butanols
Segmented copolymer (as Tergitol XH) 1.60
Dimethylbenzene 4.75
Mono chloro benzene 86.65
100.00
C. compound 43 2.5
The free acid of compound organophosphate or fragrance
The hydrophobic alkali of family or aliphatics is (as GAFAC
RE-610, GAF register of company trade mark) 4.0
Polyoxyethylene/polyoxypropylene and butanols
Segmented copolymer (as Tergitol XH,
Union Carbide register of company trade mark) 1.5
Pimelinketone 5.5
Perfume compound 200 86.5
100.00
Weight percent
D. compound 52 5.0
The free acid of compound organophosphate or fragrance
The hydrophobic alkali of family or aliphatics (as, GAFAC
RE-610） 3.00
Polyoxyethylene/polyoxypropylene and butanols
Segmented copolymer (as Tergitol XH) 2.0
Phenol 5.0
Mono chloro benzene 85.0
100.0
E. compound 53 1.50
The free acid of compound organophosphate or fragrance
The hydrophobic alkali of family or aliphatics (as, GAFAC
RE-610, GAF register of company trade mark) 4.50
Polyoxyethylene/polypropylene and butanols
Segmented copolymer is (as Tergitol XH, Union
Carbide register of company trade mark) 1.00
Isophorone 5.34
Emerset 2301 87.66
100.00
F. compound 54 4.50
The free acid of compound organophosphate or aromatic series
Or the hydrophobic alkali of aliphatics (as GAFAC RE-610) 3.00
Polyoxyethylene/polyoxypropylene and butanols embedding
Section multipolymer (as Tergitol XH) 2.00
Pimelinketone 4.75
Gamma-butyrolactone 85.75
100.00
The II flowing agent
Weight percent
A. compound 58 25.0
Xanthene glue 0.3
1,2 ethylene glycol 10.0
Sodium lignosulfonate 3.5
Sodium N-Methyl-N-oleyl
taurate 1.0
Water 60.2
100.00
B. compound 59 45.0
Xanthene glue 0.2
Magnesium aluminum silicate 0.2
Alkyl aryl sulfonate 3.5
Propylene glycol 7.0
Water 44.1
100.00
C. compound 66 23.0
Xanthene glue 0.3
Propylene glycol 10.0
Sodium lignosulfonate 3.5
Alkyl aryl sulfonate (as Morwet D-425) 2.0
Water 61.2
100.00
D. compound 81 45.0
Magnesium aluminum silicate 0.3
1,2 ethylene glycol 7.0
Alkyl aryl sulfonate 3.5
The EO/PO segmented copolymer is (as Pluronic
P-104） 1.0
Water 43.2
100.00
The III wettable powder
Weight percent
A. compound 83 25.0
Sodium lignosulfonate 5.0
Kaolin 60.0
Soft silica (synthesizing) 10.0
100.00
B. compound 85 80.0
Dioctyl sulfo-sodium succinate 1.5
Alkyl aryl sulfonate 3.5
Kaolin 5.0
Soft silica (synthesizing) 10.0
100.00
C. compound 93 10.0
Sodium lignosulfonate 3.0
Sodium N-Methyl-N-oleyl-taurate 1.0
Soft silica (synthesizing) 10.0
Kaolin 76.0
100.00
D. compound 96 30.0
Sodium lignosulfonate 4.0
Dioctyl sulfo-sodium succinate 1.0
U.S.'s atlapulgite 60.0
Soft silica (synthesizing) 5.0
100.00
E. compound 102 75.0
Dioctyl sulfo-sodium succinate 1.25
Sodium lignosulfonate 3.0
Kaolin 10.75
Soft silica (synthesizing) 10.0
100.00
F. compound 106 15.0
Sodium lignosulfonate 3.0
Sodium N-methyl-N-oleyl-taurate 1.0
Soft silica (synthesizing) 10.0
Kaolin 71.0
100.00
The IV granula
Weight percent
A. compound 36 15.0
Dipropylene glycol 5.0
Particle U.S. atlapulgite (24/48 order) 80.0
100.00
B. compound 43 5.0
1,2 ethylene glycol 15.0
Granular polynite (24/48 order) 80.0
100.00
C. compound 49 1.0
1,2 ethylene glycol 5.0
Granular pyrophyllite (24/48 order) 94.0
100.00
D. compound 52 5.0
Dipropylene glycol 15.0
Granular pyrophyllite (24/48 order) 80.0
100.00
E. compound 53 20.0
Granular wilkinite (24/48 order) 80.0
100.00
F. compound 54 20.0
Soft silica (synthesizing) 1.0
Granular polynite (24/48 order) 79.0
100.00
G. compound 58 5.0
1,2 ethylene glycol 10.0
Granular polynite (24/48 order) 85.0
100.00
H. compound 59 10.0
Dipropylene glycol 10.0
Granular wilkinite (30/60 order) 80.0
100.00
V. the suspension agent enriching agent
Weight percent
A. compound 66 32.5
Sodium naphthalene-formaldehyde condensation products (Morwet D-425) 3.0
Propylene glycol 10.0
Di-isopropyl sodium naphthalene sulfonate (Morwet IP) 1.0
Xanthene glue (Kelzan S) 0.2
Water 52.3
100.00
B. compound 81 37.0
Sodium lignosulfonate (Polyfon H) 5.0
EO/PO segmented copolymer (Pluronic P-105) 2.0
Propylene glycol 10.0
Xanthene glue 0.2
Water 45.8
100.00
C. compound 83 25.0
Sodium lignosulfonate (Polyfon H) 4.0
Sodium N-Methyl-N-oleyl taurate 1.0
（Igepon T-77）
1,2 ethylene glycol 10.0
Xanthene glue (Rhodopol MD50) 0.2
Magnesium aluminum silicate (Van Gel-B) 0.2
Water 59.6
100.00
D. compound 85 30.0
Naphthalenesulfonic acid-formaldehyde condensate 5.0
Glycerine 8.0
Methylcellulose gum (Methocel Al5C) 0.3
Magnesium aluminum silicate (Van Gel B) 0.2
Water 56.5
100.00
E. compound 93 33.0
Nonyl phenol ethoxylate 9.5mole EO
Sterox NJ 1.0
Sodium lignosulfonate (Reax 88B) 4.0
1,2 ethylene glycol 10.0
Xanthene glue 0.2
Water 51.8
100.00
F. compound 96 34.0
Sodium lignosulfonate (Polyfon F) 10.0
1,2 ethylene glycol 10.0
Xanthene glue 0.1
Water 45.9
100.00
G. compound 102 30.0
Naphthalenesulfonic acid-formaldehyde condensate 10.0
Propylene glycol 7.0
Snelling Grade wilkinite 0.5
Kilfoam 0.5
Water 52.0
100.00
The VI microcapsule
(active ingredient is encapsulated in the polymeric shells)
Weight percent
A. compound 69 4.0
Polyureas housing 0.4
Reax
The 88B(dispersion agent) 1.0
The NaCl(ionogen) 5.0
Water 89.6
100.00
B. compound 81 0.5
Polyureas housing 6.82
Reax
The C-21(dispersion agent) 1.0
NaNO
3(ionogen) 5.0
Perfume compound 200(solvent) 45.0
Water 41.68
100.00
C. compound 130 1.0
Polyureas housing 7.0
Reax
C-21 2.0
NaCl 10.0
Dimethylbenzene 40.0
Water 40.0
100.00
D. compound 63 48.0
Polyureas housing 4.8
Reax
88B 3.0
NaCl 15.0
Kerosene 29.2
100.0
Weight percent
E. compound 74 40.0
Polyureas housing 6.5
Reax
88B 2.0
NaNO
310.5
Solvent 25.0
Water 16.0
100.0
F. compound 157 10.0
Polyureas housing 8.5
Reax
C-21 1.5
NaCl 6.0
Solvent 20.0
Water 54.0
100.00
When the present invention uses, the significant quantity The compounds of this invention is applied to the soil that contains seed or nutrition propagule or is admixed in the soil media with any short-cut method.When being applied to soil, liquid or granulated solid composition can be undertaken, as motor duster, spraying gun (boom) and hand sprayer and spraying duster by ordinary method.Composition is because the validity of its low dosage, also can pulvis or sprays utilize aircraft to use.The accurate amount of the active ingredient that uses relies on multiple factor, comprises floristics and corresponding vegetative period, soil type and environment, rainfall amount and used particular compound.Before selecting bud, behind the bud and during soil application, normally used dosage is about 0.0005kg/ha(0.5g/ha) to 11.2kg/ha.Preferred dose is about 0.001kg/ha(1.0g/ha) to about 0.50kg/ha(500g/ha).In some cases, need the lower or higher ratio of using.Those skilled in the art comprise the foregoing description according to this specification sheets, are easy to the ratio of using of determining that the best is used under the various conditions.
Terminology used here " soil " is meant generalized, comprises the Dictionary as Webster ' s New International, Second Edition, Unabridged(1961) in defined various " soil " commonly used.Therefore, this term refers to make crop to take root any material or the medium of growth, not only comprises soil but also comprises the compost that is suitable for helping plant-growth, fertilizer, wet-milling, vegetable mould, loam, mud, sludge, clay, sand and analogue thereof.
Although the present invention has described specific embodiments of the present invention, these aspect contents are not limited thereto.A part of the present invention all can be thought in the various equivalents, variation and the improvement aspect that do not depart from main points of the present invention and the scope.
Claims (33)
1, formula I compound:
Wherein:
R
1Be hydrogen, use R
4The C that group replaces arbitrarily
1-5Alkyl; Use C
1-4The C that alkyl replaces arbitrarily
3-8Cycloalkyl or cycloalkenyl group;
R
2Be to use R
4The C that group replaces arbitrarily
1-5Alkyl;
R
3It is hydrogen or halogen; And
R
4Be hydrogen, C
1-8Alkyl, haloalkyl, alkylthio, alkoxyalkyl or multi-alkoxy alkyl, C
3-8Cycloalkyl, cycloalkenyl group, cycloalkylalkyl or cycloalkenyl alkyl;
C
2-8Alkenyl or alkynyl; Formamyl, halogen, amino, nitro, cyano group, hydroxyl contains 1-4 O, S (O)
mAnd/or the heteroatomic C of N
4-10Heterocycle, C
6-12Aryl, aralkyl or alkaryl ,-CXYR
8,-CXR
9,-CH
2OCOR
10,-YR
11,-NR
12R
13, or any two R
4Group can by saturated and/or undersaturated carbon,
And/or the heteroatoms bonding forms and to have the nearly heterocycle of 9 links, and this heterocycle can be by any described R
4Group replaces, or by with any described R
4The described R that does not comprise itself that group replaces
4Group or R
8-13Group replaces; Its condition is as described two R
4Group passes through heteroatoms
During bonding, described heterocycle has six links at least;
X is O, S (O)
m, NR
14Or CR
15R
16
Y is O or S (O)
mOr NR
17
R
8-R
17Be described R
4In the group one;
M is 0-2; And
N is 0-5.
2, formula II compound:
Wherein:
R
1, R
2And R
3Suc as formula defining in the I;
R
5Be described R independently
3In the group one, and;
R
6And R
7Be described R independently
4In the group one or in conjunction with forming the heterocycle that has 9 joints nearly and contain O, N and/or S atom, this ring can be had separately nearly that alkyl, haloalkyl, alkoxyl group, alkenyl or the alkynyl of 4 carbon atoms replace; Its condition is as described two R
6And R
7Group passes through heteroatoms
During bonding, described heterocycle has six links at least.
3, formula III compound:
Wherein:
R
1And R
2Be C
1-5Alkyl;
R
3And R
5Be hydrogen, bromine, chlorine or fluorine;
R
6Be R
5Group or nitro;
R
7Be R
4Group; Or
R
6And R
7By-OCH
2(C=O)-N-(R
4)-bonding forms the condensed six-membered ring.
4, according to the compound of claim 3, wherein:
R
1And R
2It is methyl;
R
3Be hydrogen, bromine or chlorine;
R
5Be chlorine or fluorine;
R
6Be chlorine, fluorine or nitro;
R
7Be suc as formula the YR that defines in the I
11Group; Or
R
6And R
7By-OCH
2(C=O)-the N-(proyl)-bonding obtains the condensed six-ring.
5, the compound according to claim 1 is selected from:
4-chloro-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group)-phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
6-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-7-fluoro-4-(2-proyl)-2H-1, the 4-benzoxazine-3-(4H)-ketone
(5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester
(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester
2-(5-(4-bromo-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate and
2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate.
6, phenyl 4-chloro-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group))-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles.
7, phenyl 4-bromo-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group))-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles.
8,2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate.
9, (5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester.
10, herbicidal composition, it comprises the formula I compound of auxiliary agent and herbicidally effective amount:
Ⅰ
Wherein:
R
1Be hydrogen, use R
4The C that group replaces arbitrarily
1-5Alkyl; Use C
1-4The C that alkyl replaces arbitrarily
3-8Cycloalkyl or cycloalkenyl group;
R
2Be to use R
4The C that group replaces arbitrarily
1-5Alkyl;
R
3It is hydrogen or halogen; And
R
4Be hydrogen, C
1-8Alkyl, haloalkyl, alkylthio, alkoxyalkyl or multi-alkoxy alkyl, C
3-8Cycloalkyl, cycloalkenyl group, cycloalkylalkyl or cycloalkenyl alkyl, C
2-8Alkenyl or alkynyl; Formamyl, halogen, amino, nitro, cyano group, hydroxyl contains 1-4 O, S(O)
mAnd/or the heteroatomic C of N
4-10Heterocycle, C
6-12Aryl, aralkyl or alkaryl ,-CXYR
8,-CXYR
9,-CH
2OCOR
10,-YR
11,-NR
12R
13, or any two R
4Group can by saturated and/or undersaturated carbon,
And/or the heteroatoms bonding forms and to have the nearly heterocycle of 9 links, and this heterocycle can be by any described R
4Group replaces, or by with any described R
4The described R that does not comprise itself that group replaces
4Group or R
8-13Group replaces; Its condition is as described two R
4Group passes through heteroatoms
During bonding, described heterocycle has six links at least;
X is O, S(O)
m, NR
14Or CR
15R
16;
Y is O or S(O)
mOr NR
17;
R
8-R
17Be described R
4In the group one;
M is 0-2; And
N is 0-5.
11, herbicidal composition, it comprises the formula II compound of auxiliary agent and herbicidally effective amount:
Wherein:
R
1, R
2And R
3Suc as formula defining in the I;
R
5Be described R independently
3In the group one; And
R
6And R
7Be described R independently
4In the group one or in conjunction with forming the heterocycle that has 9 joints nearly and contain O, N and/or S atom, this ring can be had separately nearly that alkyl, haloalkyl, alkoxyl group, alkenyl or the alkynyl of 4 carbon atoms replace; Its condition is as described two R
6And R
7Group passes through heteroatoms
During bonding, described heterocycle has six links at least.
12, herbicidal composition, it comprises the formula III compound of auxiliary agent and herbicidally effective amount:
Wherein:
R
1And R
2Be C
1-5Alkyl;
R
3And R
5Be hydrogen, bromine, chlorine or fluorine;
R
6Be R
5Group or nitro;
R
7Be R
4Group; Or
R
6And R
7By-OCH
2(C=O)-N-(R
4)-bonding forms the condensed six-membered ring.
13, according to the composition of claim 12, in the wherein said compound:
R
1And R
2It is methyl;
R
3Be hydrogen, bromine or chlorine;
R
5Be chlorine or fluorine;
R
6Be chlorine, fluorine or nitro;
R
7Be suc as formula the YR that defines in the I
11Group; Or
R
6And R
7By-OCH
2(C=O)-the N-(proyl)-bonding obtains condensed 6 joint ring.
14, according to the composition of claim 10, wherein said compound is selected from:
4-chloro-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
6-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-7-fluoro-4-(2-proyl)-2H-1, the 4-benzoxazine-3-(4H)-ketone
(5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester
(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester
2-(5-(4-bromo-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate and
2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate.
15, herbicidal composition, it comprises 4-chloro-3-[1-fluoro-4-chloro-5-(2-third alkynyloxy group of auxiliary agent and herbicidally effective amount) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles.
16, herbicidal composition, it comprises 4-bromo-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group of auxiliary agent and herbicidally effective amount) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles.
17, herbicidal composition, it comprises the 2-(5-(4-chloro-1-methyl-5-(methylsulfonyl of auxiliary agent and herbicidally effective amount)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate.
18, herbicidal composition, it comprises (5-(4-chloro-1-methyl-5-(the methylsulfonyl)-1H-pyrazole-3-yl of auxiliary agent and herbicidally effective amount)-2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester.
19, remove the method for undesirable plant in the crop, it comprises formula I compound from herbicidally effective amount to its place that use:
Wherein:
R
1Be hydrogen, use R
4The C that group replaces arbitrarily
1-5Alkyl; Use C
1-4The C that alkyl replaces arbitrarily
3-8Cycloalkyl or cycloalkenyl group;
R
2Be to use R
4The C that group replaces arbitrarily
1-5Alkyl;
R
3Be hydrogen or halogen, and
R
4Be hydrogen, C
1-8Alkyl, haloalkyl, alkylthio, alkoxyalkyl or multi-alkoxy alkyl, C
3-8Cycloalkyl, cycloalkenyl group, cycloalkylalkyl or cycloalkenyl alkyl, C
2-8Alkenyl or alkynyl; Formamyl, halogen, amino, nitro, cyano group, hydroxyl contains 1-4 O, S(O)
mAnd/or the heteroatomic C of N
4-10Heterocycle, C
6-12Aryl, aralkyl or alkaryl ,-CXYR
8,-CXR
9,-CH
2OCOR
10,-YR
11,-NR
12R
13, or any two R
4Group can by saturated and/or undersaturated carbon,
And/or the heteroatoms bonding forms and to have the nearly heterocycle of 9 links, and this heterocycle can be by any described R
4Group replaces, or by with any described R
4The described R that does not comprise itself that group replaces
4Group or R
8-13Group replaces, and its condition is as described two R
4Group passes through heteroatoms
During bonding, described heterocycle has six links at least;
X is O, S(O)
m, NR
14Or CR
15R
16;
Y is O or S(O)
mOr NR
17;
R
8-R
17Be described R
4In the group one;
M is 0-2; And
N is 0-5.
20, remove the method for undesirable plant in the crop, it comprises formula II compound from herbicidally effective amount to its place that use:
Wherein:
R
1, R
2And R
3Suc as formula defining in the I;
R
5Be described R independently
3In the group one; And
R
6And R
7Be described R independently
4In the group one or in conjunction with forming the heterocycle that has 9 joints nearly and contain O, N and/or S atom, this ring can be had separately nearly that alkyl, haloalkyl, alkoxyl group, alkenyl or the alkynyl of 4 carbon atoms replace; Its condition is as described two R
6And R
7Group passes through heteroatoms
During bonding, described heterocycle has six links at least.
21, remove the method for undesirable plant in the crop, it comprises formula III compound from herbicidally effective amount to its place that use:
Wherein:
R
1And R
2Be C
1-5Alkyl;
R
3And R
5Be hydrogen, bromine, chlorine or fluorine;
R
6Be R
5Group or nitro;
R
7Be R
4Group; Or
R
6And R
7By-OCH
2(C=O)-N-(R
4)-bonding forms the condensed six-membered ring.
22, according to the method for claim 21, in the wherein said compound:
R
1And R
2It is methyl;
R
3Be hydrogen, bromine or chlorine;
R
5Be chlorine or fluorine;
R
6Be chlorine, fluorine or nitro;
R
7Be suc as formula the YR that defines in the I
11Group; Or
R
6And R
7By-OCH
2(C=O)-the N-(proyl)-bonding obtains condensed 6 joint ring.
23, according to the method for claim 19, wherein said compound is selected from:
4-chloro-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-third alkynyloxy group) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxy ethoxy) phenyl)-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles
6-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-7-fluoro-4-(2-proyl)-2H-1, the 4-benzoxazine-3-(4H)-ketone
(5-(4-bromo-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester
(5-(4-chloro-1-methyl-5-(methylsulfonyl)-1H-pyrazole-3-yl)-and 2-chloro-4-fluorophenoxy) acetate 1-methyl ethyl ester
2-(5-(4-bromo-1-methyl-5-(methylsulfonyl)-and 1H-pyrazole-3-yl-2-chloro-4-fluorophenoxy) ethyl propionate
2-(5-(4-chloro-1-methyl-5-(methylsulfonyl)-the 1H-pyrazole-3-yl)-2-chloro-4-fluorophenoxy) ethyl propionate.
24, remove the method for undesirable plant in the crop, it comprises 4-chloro-3-[2-fluoro-4-chloro-5-(2-third alkynyloxy group from herbicidally effective amount to its place that use) phenyl]-1-methyl-5-(methylsulfonyl)-the 1H-pyrazoles.
25, the method for preparation, it comprises according to following reaction formula makes formula B compound and oxidant reaction:
Wherein:
R
1Be hydrogen, use R
4The C that group replaces arbitrarily
1-5Alkyl; Use C
1-4The C that alkyl replaces arbitrarily
3-8Cycloalkyl or cycloalkenyl group;
R
2Be to use R
4The C that group replaces arbitrarily
1-5Alkyl;
R
3It is hydrogen or halogen; And
R
4Be hydrogen, C
1-8Alkyl, haloalkyl, alkylthio, alkoxyalkyl or multi-alkoxy alkyl, C
3-8Cycloalkyl, cycloalkenyl group, cycloalkylalkyl or cycloalkenyl alkyl; C
2-8Alkenyl or alkynyl; Formamyl, halogen, amino, nitro, cyano group, hydroxyl contains 1-4 O, S(O)
mAnd/or the heteroatomic C of N
4-10Heterocycle, C
6-12Aryl, aralkyl or alkaryl ,-CXYR
8,-CXR
9,-CH
2OCOR
10,-YR
11,-NR
12R
13, or any two R
4Group can by saturated and/or undersaturated carbon,
And/or heteroatomic bond has the nearly heterocycle of 9 links in conjunction with formation, and this heterocycle can be by any described R
4Group replaces, or by with any described R
4The described R that does not comprise itself that group replaces
4Group or R
8-13Group replaces; Its condition is as described two R
4Group passes through heteroatoms
During bonding, described heterocycle has six links at least;
X is O, S(O)
m, NR
14Or CR
15R
16;
Y is O or S(O)
mOr NR
17;
R
8-R
17Be described R
4In the group one;
M is 0-2; And
N is 0-5.
26, according to the method for claim 25, wherein said formula I compound is the defined compound of formula II:
Wherein:
R
1, R
2And R
3Suc as formula defining in the I:
R
5Be described R independently
3In the group one, and
R
6And R
7Be described R independently
4In the group one or in conjunction with forming the heterocycle that has 9 joints nearly and contain O, N and/or S atom, this ring can be had separately nearly that alkyl, haloalkyl, alkoxyl group, alkenyl or the alkynyl of 4 carbon atoms replace; Its condition is as described two R
6And R
7Group passes through heteroatoms
During bonding, described heterocycle has six links at least.
27, according to the method for claim 25, wherein said formula I compound is the defined compound of formula III:
Wherein:
R
1And R
2Be C
1-5Alkyl;
R
3And R
5Be hydrogen, bromine, chlorine or fluorine;
R
6Be R
5Group or nitro;
R
7Be R
4Group; Or
R
6And R
7By-OCH
2(C=O)-N-(R
4)-bonding forms the condensed six-membered ring.
28, according to the method for claim 27, wherein:
R
1And R
2It is methyl;
R
3Be hydrogen, bromine or chlorine;
R
5Be chlorine or fluorine;
R
6Be chlorine, fluorine or nitro; And
R
7Be the YR that defines in the formula I
11Group.
29, preparation R
3Be the method for the formula I compound of halogen, it comprises R
3Be the formula I compound and the halogenating agent reaction of hydrogen.
30, according to the method for claim 29, be R wherein by the described formula I compound that halogenation method makes
3The defined compound of formula III for halogen.
31, according to the method for claim 30, R wherein
1And R
2Be methyl, R
5Be chlorine or fluorine and R
6Be chlorine, fluorine or nitro.
32, prepare described R
4One of group is-YR
11And R
11Be not the method for the formula I compound of hydrogen, it comprises corresponding R
11Be formula I compound and the acylating agent or the alkylation reactions of hydrogen.
33, according to the method for claim 32, wherein described formula I compound is R before described acidylate or alkylation
7The defined compound of formula III for-YH.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56347990A | 1990-08-06 | 1990-08-06 | |
| US563479 | 1990-08-06 | ||
| US73509191A | 1991-07-29 | 1991-07-29 | |
| US735091 | 1991-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061221A true CN1061221A (en) | 1992-05-20 |
Family
ID=27073302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108858.XA Pending CN1061221A (en) | 1990-08-06 | 1991-08-06 | The aryl alkylsulfonyl pyrazoles of the replacement of weeding |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0542872A1 (en) |
| JP (1) | JPH05509103A (en) |
| CN (1) | CN1061221A (en) |
| AU (1) | AU649474B2 (en) |
| BG (1) | BG97409A (en) |
| BR (1) | BR9106737A (en) |
| CA (1) | CA2087260A1 (en) |
| FI (1) | FI930506A0 (en) |
| HU (1) | HUT63542A (en) |
| IE (1) | IE912785A1 (en) |
| IL (1) | IL99104A0 (en) |
| MX (1) | MX9100557A (en) |
| NZ (1) | NZ239269A (en) |
| PT (1) | PT98592A (en) |
| WO (1) | WO1992002509A1 (en) |
| YU (1) | YU162291A (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5532416A (en) * | 1994-07-20 | 1996-07-02 | Monsanto Company | Benzoyl derivatives and synthesis thereof |
| TR26599A (en) * | 1992-03-17 | 1995-03-15 | Monsanto Co | MUSIC WEAR KILLER (HERBISID), SUBSTITUTED ARIL- HALOALKILPIRAZOLES. |
| AU653299B2 (en) * | 1993-02-06 | 1994-09-22 | Nihon Nohyaku Co., Ltd. | A herbicidal composition having a reduced phytotoxicity |
| NZ264574A (en) * | 1993-10-12 | 1995-12-21 | Nihon Nohyaku Co Ltd | Pesticidal aqueous suspension concentrate containing pyrazole derivatives as microparticles |
| US5880290A (en) * | 1994-01-31 | 1999-03-09 | Monsanto Company | Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity |
| DE4417837A1 (en) * | 1994-05-20 | 1995-11-23 | Basf Ag | Substituted 3-phenylpyrazoles |
| DE4419517A1 (en) * | 1994-06-03 | 1995-12-07 | Basf Ag | Substituted 3-phenylpyrazoles |
| GB9413237D0 (en) * | 1994-07-01 | 1994-08-24 | Zeneca Ltd | Herbicides |
| US5587485A (en) * | 1994-07-20 | 1996-12-24 | Monsanto Company | Heterocyclic- and carbocyclic- substituted benzoic acids and synthesis thereof |
| US5869688A (en) * | 1994-07-20 | 1999-02-09 | Monsanto Company | Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity |
| GB9422708D0 (en) * | 1994-11-10 | 1995-01-04 | Zeneca Ltd | Herbicides |
| US5639776A (en) * | 1995-01-12 | 1997-06-17 | Otsuka Kagaku Kabushiki Kaisha | 4, 5-dihydropyrazole-5-thione derivatives and miticides comprising the same |
| US6103667A (en) * | 1995-06-15 | 2000-08-15 | Novartis Corporation | Phenylpyrazole herbicides |
| AU6221796A (en) * | 1995-06-15 | 1997-01-15 | Ciba-Geigy Ag | Novel herbicides |
| DE19524623A1 (en) * | 1995-07-06 | 1997-01-09 | Basf Ag | 5-pyrazolylbenzoic acid derivatives |
| WO1997013756A1 (en) * | 1995-10-13 | 1997-04-17 | Otsuka Kagaku Kabushiki Kaisha | Pyrazole derivatives and insecticidal compositions containing the same as active ingredient |
| DE19542520A1 (en) * | 1995-11-15 | 1997-05-22 | Basf Ag | Substituted 1-methyl-3-phenylpyrazole |
| US5698708A (en) * | 1996-06-20 | 1997-12-16 | Monsanto Company | Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity |
| WO1998005649A1 (en) | 1996-08-01 | 1998-02-12 | Basf Aktiengesellschaft | Substituted 3-phenyl pyrazoles |
| US6054413A (en) * | 1996-09-19 | 2000-04-25 | Basf Aktiengesellschaft | 1-sulfonyl-3-phenylpyrazoles and their use as herbicides and for desiccating or defoliating plants |
| AU725228B2 (en) | 1996-11-12 | 2000-10-12 | Novartis Ag | Novel herbicides |
| UA53679C2 (en) | 1996-12-16 | 2003-02-17 | Басф Акцієнгезелльшафт | Substituted pyrazole-3-yl benzazoles, a process for preparation thereof (variants), a herbicide agent and a process for preparation thereof, an agent for plants desiccation and/or defoliation and a process for undesirable plants growth control and a process for plants desiccation and/or defoliation |
| BR9808398A (en) | 1997-03-21 | 2000-05-16 | Novartis Ag | Pyrazole derivatives with herbicidal activity |
| DE19803395A1 (en) * | 1998-01-29 | 1999-08-05 | Bayer Ag | Substituted heteroarylmethyl compounds |
| DE19838706A1 (en) | 1998-08-26 | 2000-03-02 | Bayer Ag | Substituted 3-aryl-pyrazoles |
| AU7284200A (en) * | 1999-09-10 | 2001-04-17 | Basf Aktiengesellschaft | Substituted pyrazol-3-ylbenzoxazinones |
| CA2408686A1 (en) * | 2000-05-15 | 2002-11-12 | Basf Aktiengesellschaft | 3-arylisothiazoles and their use as herbicides |
| AU2008236679B2 (en) | 2007-04-03 | 2013-11-28 | Fmc Corporation | Substituted benzene fungicides |
| CN103221409B (en) | 2010-10-01 | 2016-03-09 | 巴斯夫欧洲公司 | The benzo * zionoes of weeding |
| UA118118C2 (en) | 2014-02-21 | 2018-11-26 | Басф Се | Aqueous agroformulation comprising suspended pesticide, cellulose ether and thickener |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2409753A1 (en) * | 1974-03-01 | 1975-09-11 | Basf Ag | SUBSTITUTED PYRAZOLES |
-
1991
- 1991-08-02 BR BR919106737A patent/BR9106737A/en not_active Application Discontinuation
- 1991-08-02 JP JP3513763A patent/JPH05509103A/en active Pending
- 1991-08-02 AU AU84146/91A patent/AU649474B2/en not_active Expired - Fee Related
- 1991-08-02 EP EP91915235A patent/EP0542872A1/en not_active Withdrawn
- 1991-08-02 CA CA002087260A patent/CA2087260A1/en not_active Abandoned
- 1991-08-02 WO PCT/US1991/005530 patent/WO1992002509A1/en not_active Application Discontinuation
- 1991-08-02 HU HU93307A patent/HUT63542A/en unknown
- 1991-08-05 NZ NZ239269A patent/NZ239269A/en unknown
- 1991-08-06 IE IE278591A patent/IE912785A1/en unknown
- 1991-08-06 YU YU162291A patent/YU162291A/en unknown
- 1991-08-06 MX MX9100557A patent/MX9100557A/en unknown
- 1991-08-06 CN CN91108858.XA patent/CN1061221A/en active Pending
- 1991-08-06 PT PT98592A patent/PT98592A/en not_active Application Discontinuation
- 1991-08-06 IL IL99104A patent/IL99104A0/en unknown
-
1993
- 1993-02-05 BG BG97409A patent/BG97409A/en unknown
- 1993-02-05 FI FI930506A patent/FI930506A0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| MX9100557A (en) | 1992-04-01 |
| PT98592A (en) | 1992-07-31 |
| EP0542872A1 (en) | 1993-05-26 |
| IL99104A0 (en) | 1992-07-15 |
| YU162291A (en) | 1994-01-20 |
| WO1992002509A1 (en) | 1992-02-20 |
| HU9300307D0 (en) | 1993-05-28 |
| CA2087260A1 (en) | 1992-02-07 |
| AU649474B2 (en) | 1994-05-26 |
| FI930506A (en) | 1993-02-05 |
| IE912785A1 (en) | 1992-02-26 |
| JPH05509103A (en) | 1993-12-16 |
| AU8414691A (en) | 1992-03-02 |
| NZ239269A (en) | 1994-05-26 |
| HUT63542A (en) | 1993-09-28 |
| FI930506A0 (en) | 1993-02-05 |
| BG97409A (en) | 1994-03-31 |
| BR9106737A (en) | 1993-08-31 |
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