CN103626708A - Novel sulfonylurea compound - Google Patents
Novel sulfonylurea compound Download PDFInfo
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- CN103626708A CN103626708A CN201310694756.6A CN201310694756A CN103626708A CN 103626708 A CN103626708 A CN 103626708A CN 201310694756 A CN201310694756 A CN 201310694756A CN 103626708 A CN103626708 A CN 103626708A
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- 0 CC(C)(C)SC1=C(*)*C(*)=C*1 Chemical compound CC(C)(C)SC1=C(*)*C(*)=C*1 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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Abstract
The invention discloses a novel sulfonylurea compound. The structural formula (I) of the novel sulfonylurea compound is as shown in the specification. The novel sulfonylurea compound disclosed by the invention has excellent characteristics of high herbicidal activity, high degradation velocity, few residues and safety for afterreap crops, can serve as a candidate molecule of a novel herbicide and can be used for weed control in soybean fields, wheat fields and the like.
Description
It is 201310005172.3 that the application requires to submit the application number of Patent Office of the People's Republic of China on January 7th, 2013, and its denomination of invention is the right of priority of the Chinese patent application of " a kind of sulfonyl urea compound ", and its partial content is by reference in conjunction with in this application.
Technical field
The present invention relates to organic compound technical field, relate in particular to a kind of sulfonylurea compound.
Background technology
Sulfonyl urea compound started to be applied to agricultural as weedicide the latter stage seventies, as reports such as Levitt in 1978, after green sulphur grand (chlorsulfuron) carries out before seedling soil treatment or seedling with extremely low consumption, cauline leaf is processed, and can effectively prevent and treat wheat class and the most of weeds of flax field.Because sulfonyl urea compound has very high activity as weedicide, researchist has just developed the weedicide kind of a series of sulfonyl urea compound subsequently.
As weedicide, development is exceedingly fast sulfonyl urea compound, at various crop fields, is widely used, and current existing sulfonyl urea compound is comprised of aromatic ring, sulfonylurea bridge and heterocycle three parts, and its structural formula is as follows:
These compounds all have similar constitutional features, substituting group on aromatic ring has the forms such as monosubstituted or two replacements, but its substituted radical is not all in aromatic ring contraposition, and the life-time service of these sulfonyl urea compounds, caused weeds to have certain resistance to it, simultaneously their security and residual are current researchist's urgent problems, therefore, research and develop that weeding activity is high, the sulfonylurea compound of safety and low toxicity and low residue has realistic meaning.
Summary of the invention
For addressing the above problem, the present invention has changed can not introduce substituent idea in the contraposition of the aromatic ring part of sulfonyl urea compound traditionally, provides a kind of and has introduced substituent sulfonylurea compound in aromatic ring contraposition and ortho position.Sulfonylurea compound provided by the invention is introduced suitable substituent in aromatic ring contraposition and ortho position, make sulfonyl urea compound there is very high weeding activity on the one hand, accelerated on the other hand the degradation rate of sulfonyl urea compound, thereby it is high to make this compound have weeding activity, degradation speed is fast, low residue, the good characteristic to succession crop safety, can be used as the candidate molecules of new herbicides, can be used for the field weedings such as soybean, wheat.
The invention provides a kind of sulfonylurea compound, the structural formula of described sulfonyl urea compound is as shown in (I):
Wherein, R
1for amino, nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, alkyl, halo alkyl, alkylamidoalkyl, haloalkyl amide group, halogen, carboxyl, hydrazone group, phosphono, alkylsulfonyl, carbalkoxy, haloalkoxy carbonyl, two carbalkoxys, the two carbalkoxys of halo or imide,
R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
R
3, R
4for hydrogen atom, halogen, alkoxyl group, alkyl, alkylamino, aminoalkyl group, halogenated alkoxy, carbalkoxy, nitro, haloalkoxy carbonyl, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, haloalkyl is amino, halo aminoalkyl group, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
X
1, X
2, X
3for N or CH;
R
6for hydrogen atom, halogen, cyano group, nitro, hydroxyl, sulfydryl, carbalkoxy, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkane hydroxyl, halogen formyl radical, haloalkane acyl group, alkene oxygen base, alkynyloxy group, aminoalkyl group, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido or halo dialkyl amido,
R
5for hydrogen atom, sodium ion, potassium ion or ammonium ion.
Preferably, described X
1with described X
2in at least one is N, described X
3for N or CH.
Preferably, described R
1for being amino, nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl amino, dialkyl amido, halo dialkyl amido, halogen or alkyl; Described R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, dialkyl amido, haloalkyl amino or halo dialkylamino; Described R
3, described R
4for hydrogen atom, halogen, alkoxyl group, alkyl, alkylamino, aminoalkyl group, halogenated alkoxy, carbalkoxy, nitro, haloalkoxy carbonyl, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, haloalkyl amino, dialkyl amido, halo dialkyl amido, cyano group, sulfydryl or hydroxyl.
Preferably, described R
1for amino, nitro, C
1～C
4aminoalkyl group, C
1～C
4halo aminoalkyl group, hydroxyl, C
1～C
4alkane hydroxyl, C
1～C
4haloalkane hydroxyl, sulfydryl, C
1～C
4alkane sulfydryl, C
1～C
4haloalkane sulfydryl, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino, halo two (C
1～C
4alkyl) amino, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkylamidoalkyl, C
1～C
4haloalkyl amide group, fluorine atom, chlorine atom, bromine atoms, iodine atom, carboxyl, hydrazone group, phosphono, alkylsulfonyl, C
1～C
4carbalkoxy, C
1～C
4haloalkoxy carbonyl, two (C
1～C
4) two (C of carbalkoxy, halo
1～C
4) carbalkoxy or imide;
Described R
2for C
1～C
4carbalkoxy, fluorine atom, chlorine atom, bromine atoms, iodine atom, nitro, C
1～C
4haloalkoxy carbonyl, C
1～C
4alkoxyl group, C
1～C
4halogenated alkoxy, C
1～C
4alkane mercapto carbonyl, C
1～C
4haloalkane mercapto carbonyl, C
1～C
4alkyl sulphonyl, C
1～C
4halogenated alkyl sulfonyl, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkylamidoalkyl, C
1～C
4haloalkyl amide group, C
1～C
4alkyloyl, C
1～C
4haloalkane acyl group, amino, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino, halo two (C
1～C
4alkyl) amino, C
2～C
4thiazolinyl, C
2～C
4haloalkenyl group, C
2～C
4alkynyl, C
2～C
4halo alkynyl, C
3～C
10cycloalkyl, C
3～C
10halogenated cycloalkyl, C
2～C
4alkene oxygen base, C
2～C
4alkynyloxy group, C
1～C
4alkylthio, C
1～C
4halogenated alkylthio, C
1～C
4alkyl sulfonyl-amino, C
1～C
4alkyl-carbonyl-amino, C
6～C
10aryl, C
6～C
10substituted aryl, cyano group, sulfydryl, C
1～C
4aminoalkyl group, C
1～C
44-nitro alkyl, hydroxyl, carboxyl or sulfonic group;
Described R
3, described R
4for hydrogen atom, C
1～C
4carbalkoxy, fluorine atom, chlorine atom, bromine atoms, iodine atom, nitro, C
1～C
4haloalkoxy carbonyl, C
1～C
4alkoxyl group, C
1～C
4halogenated alkoxy, C
1～C
4alkane mercapto carbonyl, C
1～C
4haloalkane mercapto carbonyl, C
1～C
4alkyl sulphonyl, C
1～C
4halogenated alkyl sulfonyl, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkylamidoalkyl, C
1～C
4haloalkyl amide group, C
1～C
4alkyloyl, C
1～C
4haloalkane acyl group, amino, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino, halo two (C
1～C
4alkyl) amino, C
2～C
4thiazolinyl, C
2～C
4haloalkenyl group, C
2～C
4alkynyl, C
2～C
4halo alkynyl, C
3～C
10cycloalkyl, C
3～C
10halogenated cycloalkyl, C
2～C
4alkene oxygen base, C
2～C
4alkynyloxy group, C
1～C
4alkylthio, C
1～C
4halogenated alkylthio, C
1～C
4alkyl sulfonyl-amino, C
1～C
4alkyl-carbonyl-amino, C
6～C
10aryl, C
6～C
10substituted aryl, cyano group, sulfydryl, C
1～C
4aminoalkyl group, C
1～C
44-nitro alkyl, hydroxyl, carboxyl or sulfonic group;
Described X
1, described X
2, described X
3for N or CH;
Described R
6for hydrogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom, C
1～C
4carbalkoxy, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkoxyl group, C
1～C
4halogenated alkoxy, nitro, C
2～C
4thiazolinyl, C
2～C
4haloalkenyl group, C
2～C
4alkynyl, C
2～C
4halo alkynyl, C
3～C
10cycloalkyl, C
3～C
10halogenated cycloalkyl, hydroxyl, C
1～C
4alkane hydroxyl, halogen formyl radical, C
1～C
4haloalkane acyl group, C
2～C
4alkene oxygen base, C
2～C
4alkynyloxy group, C
1～C
4aminoalkyl group, C
1～C
4alkyl sulfonyl-amino, C
1～C
4alkyl-carbonyl-amino, C
6～C
10aryl, C
6～C
10substituted aryl, cyano group, sulfydryl, C
1～C
4alkane sulfydryl, C
1～C
4haloalkane sulfydryl, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino or halo two (C
1～C
4alkyl) amino;
Described R
5for hydrogen atom, sodium ion, potassium ion or ammonium ion.
Preferably, described R
1for amino, nitro, hydroxyl, sulfydryl, C
1～C
2aminoalkyl group, C
1～C
2halo aminoalkyl group, C
1～C
2alkane hydroxyl, C
1～C
2haloalkane hydroxyl, C
1～C
2alkane sulfydryl, C
1～C
2haloalkane sulfydryl, C
1～C
2alkylamino, C
1～C
2haloalkyl is amino, two (C
1～C
2alkyl) amino, halo two (C
1～C
2alkyl) amino, fluorine atom, chlorine atom, bromine atoms or iodine atom; Described R
2for C
1～C
2carbalkoxy, fluorine atom, chlorine atom, bromine atoms or iodine atom; Described R
3, described R
4for hydrogen atom, alkoxyl group, fluorine atom, chlorine atom, bromine atoms, iodine atom or C
1～C
2alkyl; Described X
1, described X
2, described X
3for N or CH; Described R
6for hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom; Described R
5for hydrogen atom, sodium ion or potassium ion.
Preferably, described R
1for alkyl, halogen, hydroxyl, amino, nitro, carboxyl, alkylamino, dialkyl amido or alkane hydroxyl; Described R
2for carbalkoxy or halogen; Described R
3, described R
4for alkoxyl group or halogen; Described X
1, described X
2, described X
3for N or CH; Described R
5with described R
6be hydrogen atom.
More preferably, described R
1for nitro, hydroxyl, amino, C
1～C
4alkylamino or two (C
1～C
4alkyl) amino; Described R
2for chlorine atom or C
1～C
4carbalkoxy; Described R
3, described R
4for methoxyl group or chlorine atom; Described X
1with described X
2be CH, described X
3for N or CH; Described R
5with described R
6be hydrogen atom.
Further, more preferably, described R
1for nitro, hydroxyl, amino, C
1～C
4alkylamino or two (C
1～C
4alkyl) amino; Described R
2for chlorine atom, methoxycarbonyl or ethoxycarbonyl; Described R
3, described R
4for methoxyl group or chlorine atom; Described X
1with described X
2be CH, described X
3for N or CH; Described R
5with described R
6be hydrogen atom.
The preparation method of sulfonylurea compound provided by the invention, comprises the steps:
(1) by structural formula, be
compd A join in the tert.-butyl mercaptan solution that contains DMSO and potassium hydroxide, obtain reaction solution, described reaction solution reacts, and after question response stops, filtering, separating-purifying reaction solution, obtains structural formula and is
compd B, wherein, R
1for nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, alkyl, halo alkyl, alkylamidoalkyl, haloalkyl amide group, halogen, carboxyl, hydrazone group, phosphono, alkylsulfonyl, carbalkoxy, haloalkoxy carbonyl, two carbalkoxys, the two carbalkoxys of halo or imide,
R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
X
1, X
2for N or CH;
(2) acetic acid solution of compd B is placed in to ice bath, and successively adds DMSO and contain after hydrobromic acetic acid solution, obtain reaction solution, then reaction solution is warming up to room temperature, stir and react; After question response stops, filtering, separating-purifying reaction solution, obtain structural formula and be
(3) Compound C is dissolved in the solution that contains methylene dichloride, ammonium nitrate and TMS-Cl, obtains reaction solution and react; After question response finishes, described reaction solution is cooled to room temperature, filtration, purification obtain structural formula and are
compound D;
(4) the organic nitrile solution of Compound D is dripped in containing cyanate, organic nitrile, catalyzer and structural formula be
the mixing solutions of compd E in, obtain reaction solution and react, after question response stops, filtering, separating-purifying reaction solution, obtain structural formula and be
compound F 17-hydroxy-corticosterone, wherein, R
3, R
4for hydrogen atom, carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group, R
6for hydrogen atom, halogen, carbalkoxy, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, nitro, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, hydroxyl, alkane hydroxyl, halogen formyl radical, haloalkane acyl group, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido or halo dialkyl amido, X
3for N or CH, organic nitrile is acetonitrile or propionitrile, cyanate is Zassol or potassium cyanate, catalyzer is pyridine or phase-transfer catalyst,
(5) by structural formula, be
(wherein, R
1, R
2, R
3and R
4in at least one is nitro) compound F 17-hydroxy-corticosterone
1be dissolved in the hydrochloric acid soln that contains iron powder, obtain reaction solution, described reaction solution carries out reduction reaction, is about to R
1, R
2, R
3and R
4in arbitrarily nitro reduce; After question response stops, filtering, separating-purifying reaction solution, obtain structural formula and be
(6) under room temperature, drip sodium hydroxide, potassium hydroxide or ammonia soln in the acetone soln that contains compound F 17-hydroxy-corticosterone or G, obtain reaction solution, described reaction solution carries out neutralization reaction, after question response stops, filtering, separating-purifying reaction solution, obtain structural formula and be
compound H, wherein, R
1for amino, nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, alkyl, halo alkyl, alkylamidoalkyl, haloalkyl amide group, halogen, carboxyl, hydrazone group, phosphono, alkylsulfonyl, carbalkoxy, haloalkoxy carbonyl, two carbalkoxys, the two carbalkoxys of halo or imide,
R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
R
3, R
4for hydrogen atom, carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
X
1, X
2, X
3for N or CH;
R
6for hydrogen atom, halogen, carbalkoxy, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, nitro, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, hydroxyl, alkane hydroxyl, halogen formyl radical, haloalkane acyl group, alkene oxygen base, alkynyloxy group, aminoalkyl group, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido or halo dialkyl amido,
R
5for sodium ion, potassium ion or ammonium ion;
To sum up, compound F 17-hydroxy-corticosterone, compound G and compound H form target compound (I):
Wherein, R
1for amino, nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, alkyl, halo alkyl, alkylamidoalkyl, haloalkyl amide group, halogen, carboxyl, hydrazone group, phosphono, alkylsulfonyl, carbalkoxy, haloalkoxy carbonyl, two carbalkoxys, the two carbalkoxys of halo or imide,
R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
R
3, R
4for hydrogen atom, carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
X
1, X
2, X
3for N or CH;
R
6for hydrogen atom, halogen, carbalkoxy, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, nitro, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, hydroxyl, alkane hydroxyl, halogen formyl radical, haloalkane acyl group, alkene oxygen base, alkynyloxy group, aminoalkyl group, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido or halo dialkyl amido,
R
5for hydrogen atom, sodium ion, potassium ion or ammonium ion.
Compared with prior art, the present invention has following beneficial effect:
Sulfonyl urea compound provided by the invention has been broken through the structural pattern of selected sulfonyl urea compound in the past, formed a kind of sulfonylurea compound, on the contraposition of sulfonyl urea compound aromatic ring and ortho position, introduce substituting group, or change aromatic ring into pyridine or pyrazine, and introduce substituting group on pyridine or pyrazine contraposition and ortho position, can increase the combination energy of sulfonyl urea compound molecule and target proteins, make sulfonyl urea compound there is very high weeding activity on the one hand, accelerated on the other hand sulfonyl urea compound degradation rate, thereby it is high to make this class sulfonylurea compound have weeding activity, degradation speed is fast, low residue, good characteristic to succession crop safety, can be used as the candidate molecules of new herbicides, for soybean, the field weedings such as wheat.And, change aromatic ring into pyridine or pyrazine, the activity of its corresponding compound, selectivity, security and residual are also very good, can be as the candidate molecules of new herbicides.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with accompanying drawing and preferred embodiment, the present invention is described in further detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used in restriction the present invention.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Fig. 1 is the preparation flow schematic diagram of the target compound that provides of the embodiment of the present invention 1～embodiment 3; In conjunction with Fig. 1, embodiment 1～embodiment 3 provides respectively 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-nitrophenyl) solsonylurea compounds, 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) solsonylurea compounds and 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea sodium salt compound.
Embodiment 1
The present embodiment provides 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-nitrophenyl) solsonylurea compounds, and its preparation method comprises the steps:
(1) synthetic (2-methoxycarbonyl-4-nitro) phenyl tertiary butyl thioether
First, get one of 500mL round-bottomed flask, put into oil bath, setting oil bath temperature is 25 ℃, at N
2under protection is lower, adds respectively 20mLDMSO and 4.8gKOH, stir, toward round-bottomed flask in, add 12mL tert.-butyl mercaptan after crossing 20min, continue stirring 30min; Then in round-bottomed flask, add 15.68g2-chloro-5-nitrobenzoic acid methyl esters, after adding, setting oil bath temperature is 110 ℃, has yellow solid to generate in temperature-rise period, after arriving 110 ℃, temperature reacts 90min, then stop heating, make flask be down to room temperature,, there is yellow black solid at the bottle end; Water toward adding 200mL in round-bottomed flask, has yellow solid to separate out, and stirs, and suction filtration, washes with water and obtain yellow solid; Filtrate is with the extraction of 400mL ethyl acetate, combined ethyl acetate filtrate, and with the water washing of 400mL saturated common salt, and then add anhydrous sodium sulphate, and dried overnight, filters, and vacuum rotary steam steams solvent and also obtains yellow solid, is dried; Obtain altogether 16.8g yellow solid and be (2-methoxycarbonyl-4-nitro) phenyl tertiary butyl thioether;
(2) synthesize 2,2 '-dithio two (4-nitrobenzene methyl)
First, (2-methoxycarbonyl-4-nitro) the phenyl tertiary butyl thioether making in 9.43g step (1) is dissolved in to 12mL acetic acid and is placed in 100mL flask, obtain mixing solutions, then this mixing solutions is placed in to ice bath, add 2.5mLDMSO, continue to be placed in ice bath, then toward the HBr acetic acid solution that adds 18.2mL33wt% in flask, then be warming up to room temperature, stirring reaction spends the night; With TLC monitoring reaction, after reaction finishes, in bottle, add 100mL cold water, filter, obtain faint yellow solid, then wash faint yellow solid with normal hexane, then this solid is dried, obtains 6.08g solid and be 2,2 '-dithio two (4-nitrobenzene methyl);
(3) synthetic 2-methoxycarbonyl-4-nitrobenzene sulfonyl chloride
First, get in step (2), make 2, two (4-nitrobenzene methyl) 5.1g (12mmol) of 2 '-dithio are dissolved in the dichloromethane solution that 60mL contains ammonium nitrate that 5.04g (60mmol) purity is 95% and 42.3mL TMSCl (96mmol), obtain reaction solution, and this reaction solution is placed in to an airtight Glass tubing, make this reaction solution stirring reaction 15h～24h at 50 ℃, with TLC monitoring reaction; Question response finishes, and this reaction solution is cooled to room temperature, filters, and then uses respectively 200mL water and 100mL saturated aqueous common salt wash filtrate, and gained filtrate is used anhydrous Na again
2sO
4dried overnight, then decompression steams the solvent in filtrate, obtains 2.754g solid and is 2-methoxycarbonyl-4-nitrobenzene sulfonyl chloride;
(4) synthetic 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-nitrophenyl) sulfonylurea
First, at room temperature, in 100mL flask, add respectively chloro-6 methoxy pyrimidines of 2-amino-4-that 1.09g (0.0067mol) purity is 98%, the Zassol that 0.449g (0.0067mol) purity is 97%, 8mL acetonitrile and 0.5mL pyridine, be then placed in oil bath pan by 100mL flask; Taking the 2-methoxycarbonyl-4-nitrobenzene sulfonyl chloride 1.865g (0.0067mol) making in step (3) is dissolved in 4mL acetonitrile stand-by; 40～45 ℃ of oil bath pan design temperatures, when homo(io)thermism drips the acetonitrile solution of 2-methoxycarbonyl-4-nitrobenzene sulfonyl chloride during at 40～45 ℃ toward the flask in oil bath pan, after 3h dropwises, continue reaction 3h; React complete, filter, obtain the cotton-shaped solid of slightly yellowy white, then use respectively a small amount of acetonitrile and a large amount of water washing white solids, the cotton-shaped solid of white after washes clean is placed in to 80 ℃ of vacuum drying ovens dries, obtain 0.69g3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-nitrophenyl) sulfonylurea, its structural formula is as F
2shown in:
Structural Identification:
(TMS is interior mark to NMR hydrogen spectrum, CDCl
3for solvent) show that this compound contains 12 hydrogen, peak is attributed to 12.276 (s1H SO
2nH), 8.473～8.501 (m1H ArH), 8.542～8.547 (m1H ArH), 8.609～8.631 (m1H ArH), 7.453 (s1H CONH), 6.530 (s1H ArH), 4.102 (s3H OCH
3) and 4.003 (s3H COOCH
3).
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-nitrophenyl) sulfonylurea.
Embodiment 2
Synthetic 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea
First, measure 50ml water and add in 250ml there-necked flask, drip hydrochloric acid and regulate its pH value to 4～5, then add 100 order iron powder 0.5g, and heating at 100 ℃, Quick mechanical stirs 1 hour; Reduce Water Tank with Temp.-controlled temperature, 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-nitrophenyl) the sulfonylurea 0.4g that adds embodiment 1 to make at 70～80 ℃, at this temperature, react 5 hours, with oozing circle method monitoring reaction, when oozing, turn black in circle place and color is constant reacts completely; At 80-90 ℃, add saturated sodium carbonate solution and regulate its pH value to 9～10, continue to stir 0.5 hour, then filter, obtain oyster filtrate; Toward dripping pH value in filtrate, be 2～3 dilute hydrochloric acid, separate out precipitation, filtration obtains light yellow solid, use again methylene chloride-methanol recrystallization, dry obtain 0.06g yellow-green colour pressed powder and be 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea, its structural formula is as G
1shown in:
Structural Identification:
(TMS is interior mark to NMR hydrogen spectrum, CDCl
3for solvent) show that this compound contains 12 hydrogen, peak is attributed to 11.85 (s1H SO
2nH), 8.543～8.548 (m1H ArH), 8.472～8.500 (m1H ArH), 8.147～8.149 (m1H ArH), 7.260 (s1H CONH), 6.47 (s1H ArH), 4.102 (s3H OCH
3) 4.003 (s3H COOCH
3).
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea.
Embodiment 3
Synthetic 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea sodium salt
First, at room temperature, toward 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea that adds 2.225g (0.005mol) embodiment 2 to make in 100mL there-necked flask, 20mL acetone, then stir it to all dissolving, and react 30min after dripping 1g (0.006mol) 50% aqueous sodium hydroxide solution; Ice-water bath is cooled to below 0 ℃, and crystallization filters, and washes with water, collects solid, dries to obtain sodium salt 2.130g, and its structural formula is as H
1shown in:
Structural Identification:
(TMS is interior mark to NMR hydrogen spectrum, CDCl
3for solvent) show that this compound contains 12 hydrogen, peak is attributed to 8.553～8.540 (m1H ArH), 8.462～8.400 (m1H ArH), 8.127～8.119 (m1H ArH), 7.300 (s1H CONH), 6.57 (s1H ArH), 4.112 (s3H OCH
3), 4.023 (s3H COOCH
3).
The resulting material of the above-mentioned reaction of above data acknowledgement is 3-(4-chloro-6-methoxylpyrimidin-2-yl)-1-(2-methoxycarbonyl-4-aminophenyl) sulfonylurea sodium salt.
By the method in above embodiment, can composite structure formula be other particular compound in the compound of (I).
Table 1 is that structural formula is the part particular compound in the compound of (I)
For the beneficial effect of valid certificates sulfonylurea compound provided by the invention, provide relevant effect embodiment as follows.
Effect embodiment 1
The mensuration of weeding activity
The present embodiment has adopted the weeding activity of sulfonyl urea compound and chlorimuronethyl in pot-culture method mensuration table 1, in the plastics cuvette that is 10cm at diameter, put into a certain amount of soil, first water drenches, then sowing also covers certain thickness soil in the above, under room temperature, cultivate, before coming up, with plastics film, cover; Add a certain amount of water every day; Processing comprises that soil treatment (before emerging) and cauline leaf (seedling one leaf one heart stage) process two kinds; Test target is designated as purslane, lamb's-quarters, trifolium and lady's-grass; Three weeks " Invest, Then Investigate " results, measure overground part fresh weight, suppress percentage ratio (%) represent drug effect with fresh weight; Result is as shown in table 2:
Table 2: weeding activity inhibiting rate (%) contrast table of part sulfonyl urea compound and chlorimuronethyl in table 1
Note: compound number is with table 1
Result shows, sulfonyl urea compound provided by the invention has very high weeding activity.
Effect embodiment 2
Mensuration to the security of crop
Sulfonyl urea compound in the present embodiment employing pot-culture method mensuration table 1 is to the selectivity of crop and security thereof, and with existing chlorimuronethyl object as a comparison, be about to the list of several susceptibility, the seed of broadleaf weed and crop is planted in flowerpot simultaneously, through after a while, when monocotyledons has two leaves wholeheartedly, dicotyledons has three to four leaves when (comprising cotyledon), use the same method and repeat plantation, and do soil treatment and cauline leaf processing with the medicament to be measured being dissolved in innoxious solvent, processing two to three weeks " Invest, Then Investigate " results shows: before seedling or during seedling aftertreatment, while even using the compound of high dosage, compound in table 1 is to farm crop soybean, wheat safety.
Effect embodiment 3
The mensuration of residual hydrolysis
Accurately take each 6 milligrams of testing compounds, add a small amount of acetonitrile, with ultrasonic dissolved solution sample, add continue after the dual distilled water of 200 milliliters for ultrasonic dissolved solution sample, cross after the millipore filtration of 4.5 microns the preliminary examination concentration of sampling and measuring test compound immediately, then the aqueous solution is put into the thermostat container of 30 degrees Celsius, its residual quantity in water is measured at interval for 3 days, with residual quantity, to mapping sample time, every sub-sampling counterpoise is answered 3 times computerized compound transformation period in water.Mensuration mode is: get 3 milliliters of sample solutions, adding massfraction is to use respectively 30 milliliters after 50 milliliters of 2% metabisulfite solutions, 20 milliliters, 20 milliliters of methylene dichloride extract respectively 3 times, combined dichloromethane is also crossed anhydrous sodium sulfate drying mutually, methylene dichloride is closely dry at 35～40 degrees Celsius of rotary evaporations, and rubber suction bulb dries up treats that with acetonitrile constant volume to 2 milliliter HPLC measures afterwards.
Analytical data, the transformation period of learning chlorimuronethyl when pH=5 is 22.2 days, and chemical combination 1 in table 1, 2, 3, 5, 8, 16, 20, 23, 31, 33, 35, 38, 46, 50 transformation period under this pH condition were about about 5～15 days, be chemical combination 1, 2, 3, 5, 8, 16, 20, 23, 31, 33, 35, 38, 46, 50 transformation period under this pH condition were respectively 7.4 days, 8.5 my god, 11.8 days, 7.9 my god, 10.4 days, 7.6 my god, 8.1 my god, 13.7 days, 8.0 my god, 11.5 days, 8.0 my god, 12.7 days, 7.5 my god, within 8.4 days, result shows the compound 1 in table 1, 2, 3, 5, 8, 16, 20, 23, 31, 33, 35, 38, 46, 50 in water degradation speed fast compared with chlorimuronethyl, medicine is residual lower, it is potential herbicide molecular.
Certainly, the above is only indivedual example of the present invention, all according to the structure described in the present patent application the scope of the claims, principle and similar variation, all should be contained in the scope of the present patent application patent.
Claims (8)
1. a sulfonylurea compound, is characterized in that, the structural formula of described sulfonyl urea compound is as shown in (I):
Wherein, R
1for amino, nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, alkyl, halo alkyl, alkylamidoalkyl, haloalkyl amide group, halogen, carboxyl, hydrazone group, phosphono, alkylsulfonyl, carbalkoxy, haloalkoxy carbonyl, two carbalkoxys, the two carbalkoxys of halo or imide,
R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, haloalkyl is amino, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, aminoalkyl group, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
R
3, R
4for hydrogen atom, halogen, alkoxyl group, alkyl, alkylamino, aminoalkyl group, halogenated alkoxy, carbalkoxy, nitro, haloalkoxy carbonyl, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, haloalkyl is amino, halo aminoalkyl group, dialkyl amido, halo dialkyl amido, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkene oxygen base, alkynyloxy group, alkylthio, halogenated alkylthio, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, cyano group, sulfydryl, 4-nitro alkyl, hydroxyl, carboxyl or sulfonic group,
X
1, X
2, X
3for N or CH;
R
6for hydrogen atom, halogen, cyano group, nitro, hydroxyl, sulfydryl, carbalkoxy, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, thiazolinyl, haloalkenyl group, alkynyl, halo alkynyl, cycloalkyl, halogenated cycloalkyl, alkane hydroxyl, halogen formyl radical, haloalkane acyl group, alkene oxygen base, alkynyloxy group, aminoalkyl group, alkyl sulfonyl-amino, alkyl-carbonyl-amino, aryl, substituted aryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl is amino, dialkyl amido or halo dialkyl amido,
R
5for hydrogen atom, sodium ion, potassium ion or ammonium ion.
2. sulfonyl urea compound according to claim 1, is characterized in that, described X
1with described X
2in at least one is N, described X
3for N or CH.
3. sulfonyl urea compound according to claim 1 and 2, is characterized in that, described R
1for being amino, nitro, aminoalkyl group, halo aminoalkyl group, hydroxyl, alkane hydroxyl, haloalkane hydroxyl, sulfydryl, alkane sulfydryl, haloalkane sulfydryl, alkylamino, haloalkyl amino, dialkyl amido, halo dialkyl amido, halogen or alkyl; Described R
2for carbalkoxy, halogen, nitro, haloalkoxy carbonyl, alkoxyl group, halogenated alkoxy, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, alkyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, alkylamino, dialkyl amido, haloalkyl amino or halo dialkylamino; Described R
3, described R
4for hydrogen atom, halogen, alkoxyl group, alkyl, alkylamino, aminoalkyl group, halogenated alkoxy, carbalkoxy, nitro, haloalkoxy carbonyl, alkane mercapto carbonyl, haloalkane mercapto carbonyl, alkyl sulphonyl, halogenated alkyl sulfonyl, haloalkyl, alkylamidoalkyl, haloalkyl amide group, alkyloyl, haloalkane acyl group, amino, haloalkyl amino, dialkyl amido, halo dialkyl amido, cyano group, sulfydryl or hydroxyl.
4. sulfonyl urea compound according to claim 1 and 2, is characterized in that, described R
1for amino, nitro, C
1～C
4aminoalkyl group, C
1～C
4halo aminoalkyl group, hydroxyl, C
1～C
4alkane hydroxyl, C
1～C
4haloalkane hydroxyl, sulfydryl, C
1～C
4alkane sulfydryl, C
1～C
4haloalkane sulfydryl, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino, halo two (C
1～C
4alkyl) amino, phosphine acylamino, sulfonamido, guanidine radicals, amidino groups, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkylamidoalkyl, C
1～C
4haloalkyl amide group, fluorine atom, chlorine atom, bromine atoms, iodine atom, carboxyl, hydrazone group, phosphono, alkylsulfonyl, C
1～C
4carbalkoxy, C
1～C
4haloalkoxy carbonyl, two (C
1～C
4) two (C of carbalkoxy, halo
1～C
4) carbalkoxy or imide;
Described R
2for C
1～C
4carbalkoxy, fluorine atom, chlorine atom, bromine atoms, iodine atom, nitro, C
1～C
4haloalkoxy carbonyl, C
1～C
4alkoxyl group, C
1～C
4halogenated alkoxy, C
1～C
4alkane mercapto carbonyl, C
1～C
4haloalkane mercapto carbonyl, C
1～C
4alkyl sulphonyl, C
1～C
4halogenated alkyl sulfonyl, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkylamidoalkyl, C
1～C
4haloalkyl amide group, C
1～C
4alkyloyl, C
1～C
4haloalkane acyl group, amino, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino, halo two (C
1～C
4alkyl) amino, C
2～C
4thiazolinyl, C
2～C
4haloalkenyl group, C
2～C
4alkynyl, C
2～C
4halo alkynyl, C
3～C
10cycloalkyl, C
3～C
10halogenated cycloalkyl, C
2～C
4alkene oxygen base, C
2～C
4alkynyloxy group, C
1～C
4alkylthio, C
1～C
4halogenated alkylthio, C
1～C
4alkyl sulfonyl-amino, C
1～C
4alkyl-carbonyl-amino, C
6～C
10aryl, C
6～C
10substituted aryl, cyano group, sulfydryl, C
1～C
4aminoalkyl group, C
1～C
44-nitro alkyl, hydroxyl, carboxyl or sulfonic group;
Described R
3, described R
4for hydrogen atom, C
1～C
4carbalkoxy, fluorine atom, chlorine atom, bromine atoms, iodine atom, nitro, C
1～C
4haloalkoxy carbonyl, C
1～C
4alkoxyl group, C
1～C
4halogenated alkoxy, C
1～C
4alkane mercapto carbonyl, C
1～C
4haloalkane mercapto carbonyl, C
1～C
4alkyl sulphonyl, C
1～C
4halogenated alkyl sulfonyl, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkylamidoalkyl, C
1～C
4haloalkyl amide group, C
1～C
4alkyloyl, C
1～C
4haloalkane acyl group, amino, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino, halo two (C
1～C
4alkyl) amino, C
2～C
4thiazolinyl, C
2～C
4haloalkenyl group, C
2～C
4alkynyl, C
2～C
4halo alkynyl, C
3～C
10cycloalkyl, C
3～C
10halogenated cycloalkyl, C
2～C
4alkene oxygen base, C
2～C
4alkynyloxy group, C
1～C
4alkylthio, C
1～C
4halogenated alkylthio, C
1～C
4alkyl sulfonyl-amino, C
1～C
4alkyl-carbonyl-amino, C
6～C
10aryl, C
6～C
10substituted aryl, cyano group, sulfydryl, C
1～C
4aminoalkyl group, C
1～C
44-nitro alkyl, hydroxyl, carboxyl or sulfonic group;
Described X
1, described X
2, described X
3for N or CH;
Described R
6for hydrogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom, C
1～C
4carbalkoxy, C
1～C
4alkyl, C
1～C
4haloalkyl, C
1～C
4alkoxyl group, C
1～C
4halogenated alkoxy, nitro, C
2～C
4thiazolinyl, C
2～C
4haloalkenyl group, C
2～C
4alkynyl, C
2～C
4halo alkynyl, C
3～C
10cycloalkyl, C
3～C
10halogenated cycloalkyl, hydroxyl, C
1～C
4alkane hydroxyl, halogen formyl radical, C
1～C
4haloalkane acyl group, C
2～C
4alkene oxygen base, C
2～C
4alkynyloxy group, C
1～C
4aminoalkyl group, C
1～C
4alkyl sulfonyl-amino, C
1～C
4alkyl-carbonyl-amino, C
6～C
10aryl, C
6～C
10substituted aryl, cyano group, sulfydryl, C
1～C
4alkane sulfydryl, C
1～C
4haloalkane sulfydryl, C
1～C
4alkylamino, C
1～C
4haloalkyl is amino, two (C
1～C
4alkyl) amino or halo two (C
1～C
4alkyl) amino;
Described R
5for hydrogen atom, sodium ion, potassium ion or ammonium ion.
5. sulfonyl urea compound according to claim 1, is characterized in that, described R
1for amino, nitro, hydroxyl, sulfydryl, C
1～C
2aminoalkyl group, C
1～C
2halo aminoalkyl group, C
1～C
2alkane hydroxyl, C
1～C
2haloalkane hydroxyl, C
1～C
2alkane sulfydryl, C
1～C
2haloalkane sulfydryl, C
1～C
2alkylamino, C
1～C
2haloalkyl is amino, two (C
1～C
2alkyl) amino, halo two (C
1～C
2alkyl) amino, fluorine atom, chlorine atom, bromine atoms or iodine atom; Described R
2for C
1～C
2carbalkoxy, fluorine atom, chlorine atom, bromine atoms or iodine atom; Described R
3, described R
4for hydrogen atom, alkoxyl group, fluorine atom, chlorine atom, bromine atoms, iodine atom or C
1～C
2alkyl; Described X
1, described X
2, described X
3for N or CH; Described R
6for hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom; Described R
5for hydrogen atom, sodium ion or potassium ion.
6. sulfonyl urea compound according to claim 1, is characterized in that, described R
1for alkyl, halogen, hydroxyl, amino, nitro, carboxyl, alkylamino, dialkyl amido or alkane hydroxyl; Described R
2for carbalkoxy or halogen; Described R
3, described R
4for alkoxyl group or halogen; Described X
1, described X
2, described X
3for N or CH; Described R
5with described R
6be hydrogen atom.
7. sulfonyl urea compound according to claim 6, is characterized in that, described R
1for nitro, hydroxyl, amino, C
1～C
4alkylamino or two (C
1～C
4alkyl) amino; Described R
2for chlorine atom or C
1～C
4carbalkoxy; Described R
3, described R
4for methoxyl group or chlorine atom; Described X
1with described X
2be CH, described X
3for N or CH; Described R
5with described R
6be hydrogen atom.
8. sulfonyl urea compound according to claim 7, is characterized in that, described R
1for nitro, hydroxyl, amino, C
1～C
4alkylamino or two (C
1～C
4alkyl) amino; Described R
2for chlorine atom, methoxycarbonyl or ethoxycarbonyl; Described R
3, described R
4for methoxyl group or chlorine atom; Described X
1with described X
2be CH, described X
3for N or CH; Described R
5with described R
6be hydrogen atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694756.6A CN103626708B (en) | 2013-01-07 | 2013-12-16 | A kind of sulfonylurea compound |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005172.3 | 2013-01-07 | ||
| CN2013100051723A CN103073507A (en) | 2013-01-07 | 2013-01-07 | Sulfonylurea compound |
| CN201310694756.6A CN103626708B (en) | 2013-01-07 | 2013-12-16 | A kind of sulfonylurea compound |
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| CN103626708A true CN103626708A (en) | 2014-03-12 |
| CN103626708B CN103626708B (en) | 2016-01-20 |
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| CN2013100051723A Pending CN103073507A (en) | 2013-01-07 | 2013-01-07 | Sulfonylurea compound |
| CN201310694756.6A Expired - Fee Related CN103626708B (en) | 2013-01-07 | 2013-12-16 | A kind of sulfonylurea compound |
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| CN107089953A (en) * | 2017-05-10 | 2017-08-25 | 南开大学 | The research and application of one class soil degrading speed controllable novel green sulfonylurea herbicide preparation method and soil degrading |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004967A1 (en) * | 1989-10-06 | 1991-04-18 | E.I. Du Pont De Nemours And Company | Compounds useful for measuring low levels of sulfonylureas by immunoassay |
| CN1059446A (en) * | 1990-09-06 | 1992-03-18 | 希巴-盖吉股份公司 | Synergism goods and the method for Selective Control weeds |
| US5371060A (en) * | 1992-02-26 | 1994-12-06 | Ciba-Geigy Corporation | Selective herbicidal composition comprising 1,5-diphenylpyrazole-3-carboxylic acid safeners and sulfonylurea herbicides |
| CN1702064A (en) * | 2005-06-27 | 2005-11-30 | 南开大学 | Sulfonyl urea compounds and herbicidal activity thereof |
-
2013
- 2013-01-07 CN CN2013100051723A patent/CN103073507A/en active Pending
- 2013-12-16 CN CN201310694756.6A patent/CN103626708B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004967A1 (en) * | 1989-10-06 | 1991-04-18 | E.I. Du Pont De Nemours And Company | Compounds useful for measuring low levels of sulfonylureas by immunoassay |
| CN1059446A (en) * | 1990-09-06 | 1992-03-18 | 希巴-盖吉股份公司 | Synergism goods and the method for Selective Control weeds |
| US5371060A (en) * | 1992-02-26 | 1994-12-06 | Ciba-Geigy Corporation | Selective herbicidal composition comprising 1,5-diphenylpyrazole-3-carboxylic acid safeners and sulfonylurea herbicides |
| CN1702064A (en) * | 2005-06-27 | 2005-11-30 | 南开大学 | Sulfonyl urea compounds and herbicidal activity thereof |
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| Title |
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| 刘祥英等: "磺酰脲类除草剂及其安全剂研究进展", 《杂草科学》 * |
| 柴超等: "安全剂减轻磺酰脲类和咪唑啉酮类除草剂药害的作用机制", 《农药科学与管理》 * |
| 边强等: "磺酰脲类除草剂安全剂的研究进展", 《农药》 * |
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| CN103626708B (en) | 2016-01-20 |
| CN103073507A (en) | 2013-05-01 |
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