CN101041639B - 4-substituted benzene radical pyridazine compound and weed removal activity - Google Patents
4-substituted benzene radical pyridazine compound and weed removal activity Download PDFInfo
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Abstract
The invention discloses a 4-substituted phenyl pyridazine compound (III) with high weeding activity for one-year forage and broad-leaved weed, wherein R1 is H, alkyl, alkoxy, halogenated alkyl groups,halogenated alkoxy, halogen and so on; R2 is H, alkyl, alkoxy, phenyl alkoxy, hydroxy alkyl, alkoxyalkyl, halogenated alkyl groups, halogenated alkoxy, nitro group, alkylamine, dialkylamine, acetylamino and so on; R3 is H, alkyl, hydroxy alkyl, alkoxyalkyl, halogenated alkyl groups, olefin, halogenated olefin and so on; R4 is benzo oxazole, substituted benzo oxazole, benzo thiazole and so on; R5is H, alkyl, halogenated alkyl; R6 and 67 can be the same or different, which is H or alkyl.
Description
Technical field
The present invention relates to 4-substituted benzene radical pyridazine compound and weeding activity.
Background technology
Weedicide and plant hormone function influence or the common metabolism of blocking-up plant comprise photosynthesis, the biosynthesizing of carbohydrate, lipid or amino acid whose formation and special cells integral part.Bleaching herbicide can suppress the synthetic of carotenoid, and they are relevant with the function of carotenoid to the toxic action of plant.
Carotenoid in the chloroplast(id) has dual function, on the one hand in photosynthesis as absorber of light; On the other hand as the protective substance in the photosynthesis.They have obtained some active conditions in the chlorophyllous process by optical excitation.Triplet state chlorophyll and oxygen molecule effect are singlet oxygen with Conversion of energy.Singlet oxygen has very high activity, can near its any molecule of oxidation.Carotenoid can be protected chloroplast(id), but when coloured carotenoid concentration reduced, in the time of for example in the presence of bleaching herbicide, they just can not bring into play provide protection.Directly the result is exactly a photofading, that is to say, degraded chlorophyll also destroys photosynthetic film.Most of coml bleaching herbicides all are the phytoene dehydrogenases that suppress to contain in the oxygen photosynthesis.
First enzyme in the phytoene transformation is a phytoene dehydrogenase, studies show that it is the target of bleaching herbicide.Phytoene dehydrogenase is a complete membranin, it with two identical semi-symmetric phytoene molecules as substrate.Have in the organism that carotenoid forms multiple, the phytoene dehydrogenase of two kinds of different aminoacids sequences is arranged.One type exists in the higher plant body and (also exists in blue bacterium and alginite), another kind of type in bacterium and fungi, the function difference of two kinds of enzymes.Because it is different in the bacterium with the phytoene dehydrogenase in the higher plant, bleaching herbicide has natural resistance, therefore can utilize the biotechnology preferred plant to make it produce resistance to the phytoene dehydrogenase inhibitor, this will be the work of an initiative from now on, (the Sandmann G and Boger P that makes the application of phytoene dehydrogenase inhibitor more extensive, Phytoene desaturase as a target for bleaching herbicides, inHerbicide Activity:Toxicology, Biochemistry and Molecular Biology, ed by Roe RM, Burton JDand Kuhr RJ, IOS Press, Amsterdam, Netherlands.pp 1-101997).
Norflurazon is a class phytoene dehydrogenase inhibitor early of exploitation.It is a soil processing herbicide before the bud, is mainly used in and prevents and kill off many annual broadleaf weeds in citrus, cotton, Cranberries, nut, nuts and kernels, soybean, the drupe class garden, also can suppress perennial Gramineae and sedge weed.
Monsanto Company had developed a series of 3-phenyl pyridazine class weedicides in 1999, and mechanism of action is the effect that suppresses phytoene dehydrogenase, thereby reduced the synthetic of carotenoid.The structure and the active relation of 3-phenyl pyridazine are as follows: on (1) pyridazine ring alkyl or drawing electron group are arranged; (2) on phenyl ring, a position has trifluoromethyl to replace, as the inhibitor of phytoene dehydrogenase.The replacement of other position or other group all can reduce activity on the phenyl ring; (3) 6 or 4 s' replacement reduces active on the pyridazine ring; (4) variation of 5 bit substituents is influential to activity on the pyridazine ring, and activity was best when wherein substituting group was methoxyl group.Compare with methoxyl group, contain the N of nucleophilic group, S, other substituting groups that O forms have reduced the bleaching weeding activity 5 replacement.When substituting group was OCF2H, the compound that the isonomic OCH3 of specific activity replaces was low, but selective to corn.(MichaelS.South J.Heterocyclic Chem.，1999，36，301)
The pyridazine class weedicide reported in the document is most of for phenyl is substituted in 2 and 3 s' compound, and 4-phenyl replacement pyridazine class structure is not appeared in the newspapers in the literature as weedicide.
Summary of the invention
The purpose of this invention is to provide 4-substituted benzene radical pyridazine compound and their preparation method and application.Compound of the present invention has higher weeding activity to annual gramineous weed and broadleaf weeds.
The present invention is following general formula (II) compound:
Wherein,
R
1: haloalkyl;
R
2: alkyl;
R
4The benzoxazolyl of: benzoxazolyl, benzothiazolyl, pyrimidyl, replacement, benzothiazolyl, pyrimidyl;
Substituting group on benzoxazole ring, benzothiazole ring, the pyrimidine ring is alkyl, haloalkyl, halogenated alkoxy, halogen, cyano group or nitro, and substituting group quantity is 1～5;
Said alkyl is C
1～C
6Alkyl;
N=1 or 2.
Above-mentioned said R
1Be-m-CF R
2Be 6-CH
3-, R
4Be
The compounds of this invention (II) synthetic route such as Fig. 1, concrete synthetic route of the present invention is described in detail as follows:
(1) substituted acyl ethyl propionate and hydrazine hydrate mix, and its mol ratio is 1: 1～1: 2, adds a small amount of alcoholic solvent.Mixture was 0～90 ℃ of reaction 0.5～2 hour, and placement is spent the night, and obtains colourless tabular crystal, is 4,5-dihydro-6-replacement-3-pyridazinone.
(2) 4,5-dihydro-6-replacement-3-pyridazinone is dissolved in the solvent Glacial acetic acid, and dropping liquid bromine mol ratio is 1: 1～1: 3, drip off post-heating to 40～100 ℃, reflux to place after 5～60 minutes and spend the night, be the mixture of 6-replacement-3-pyridazinone and hydrogen bromide with the reaction solution suction filtration next day.6-replacement-3-the pyridazinone that makes and the mixture of hydrogen bromide are dissolved in the solvent Glacial acetic acid, and adding the anhydrous sodium acetate mol ratio is 1: 1～1: 3.Reacted 0.5～2 hour mixture heating up to 40～110 ℃.Remove solvent under reduced pressure, resistates joins in the frozen water, suction filtration, and drying obtains white solid 6-replacement-3-pyridazinone.
(3) 6-replacement-3-pyridazinone is dissolved in the solvent anhydrous tetrahydro furan, 0～70 ℃ was reacted 2～7 hours with (replacement) phenyl-magnesium-bromide down.Reactant is through hydrolysis, washing, and drying is spin-dried for solvent after column chromatography for separation, and eluent is an ethyl acetate: sherwood oil obtains 4-(substituted-phenyl)-6-replacement-3-pyridazinone and 4,5-dihydro-4-(substituted-phenyl)-6-replacement-3-pyridazinone.
(4) 4-(substituted-phenyl)-6-replacement-3-pyridazinone and potassium carbonate powder and 2-chlorine are replaced benzoxazole or 2-chlorine replace benzothiazole or 2-chlorine substituted pyrimidines with mol ratio 1: 1～3: 1～2 at solvent N, react in the N-dimethyl sulfoxide (DMSO).Temperature of reaction is 0～70 ℃, and the reaction times is 1～48 hour.Reaction afterreaction liquid uses column chromatography after organic phase is spin-dried for through neutralization, extraction, drying, obtains solid, for 3-substituted oxy-4-(substituted-phenyl)-6-replaces pyridazine.
(5) add etoh solvent in the reactor, sodium ethylate and 4-(substituted-phenyl)-6-alkyl-3-pyridazinone, mol ratio is 1: 1～1: 2, is stirred to whole dissolvings.Add the halides that 1-2 doubly measures, 0～50 ℃ was reacted 1～48 hour down.Reaction solution is spin-dried for, and resistates uses column chromatography, and obtaining solid or liquid is that N-replacement-4-substituted-phenyl-6-replaces pyridazinone.
Described application of compound as bleaching herbicide, can be prevented and kill off annual gramineous weed and broadleaf weeds.
The synthetic 4-substituted benzene radical pyridazine compound that obtains of the present invention was not reported in the literature, was brand-new compound; As bleaching herbicide, this class formation also is brand-new simultaneously.Relatively finding the back with commercial bleaching herbicide diflufenican, some compound of the present invention in barnyard grass grass and the little agar diffusion method of rape under the 10ppm albefaction effect to be higher than commercialization kind diflufenican.The present invention can be used as the weedicide of annual gramineous weed and broadleaf weeds.
Substantive distinguishing features of the present invention can be embodied from following embodiment, but it should not to be considered as be any limitation of the invention.
Embodiment:
Embodiment 1:4,5-dihydro-6-methyl-3-pyridazinone
Ethyl levulinate 42.3g and hydrazine hydrate 27.9g mix, and add small amount of ethanol and obtain uniform solution.Mixture heating up is to boiling, and the 1 hour postcooling that refluxes is to room temperature, and placement is spent the night, and obtaining colourless tabular crystal is 4,5-dihydro-6-methyl-3-pyridazinone, productive rate 96%.
Embodiment 2:6-methyl-3-pyridazinone
With 4,5-dihydro-6-methyl-3-pyridazinone 55g is dissolved among the Glacial acetic acid 120ml of new steaming, slowly splashes into liquid bromine 33ml, drip off post-heating to refluxing, place behind the backflow 15min and spend the night, obtain the mixture of 6-methyl-3-pyridazinone and hydrogen bromide with the reaction solution suction filtration next day.6-methyl-3-the pyridazinone that makes and the mixture 22.4g of hydrogen bromide are dissolved in the 85ml Glacial acetic acid, add anhydrous sodium acetate 13.5g, mixture heating up is to boiling, backflow 1h.The solvent underpressure distillation is removed, and resistates joins in the frozen water, obtains white solid, suction filtration, and drying obtains white solid 12.9g, productive rate 80%.
Embodiment 3:4-(3-trifluoromethyl)-6-methyl-3-pyridazinone
10mmol 6-methyl-3-pyridazinone is dissolved in the 50ml anhydrous tetrahydro furan, adds the tetrahydrofuran solution of the 3-trifluoromethyl magnesium bromide of 40mmol under the room temperature.Mixture heating up is to boiling, reflux after 5 hours with saturated ammonium chloride solution hydrolysis, organic phase is washed with saturated nacl aqueous solution, dry, use column chromatography after being spin-dried for solvent, eluent is an ethyl acetate: sherwood oil obtains 4-(3-trifluoromethyl)-6-methyl-3-pyridazinone and 4,5-dihydro-4-(3-trifluoromethyl)-6-methyl-3-pyridazinone, productive rate is respectively 38.58% and 16.89%.
The preparation of embodiment 4:3-benzoxazole oxygen base-4-(3-trifluoromethyl)-6-methyl pyridazine
With 0.5mmol 4-(3-trifluoromethyl)-6-methyl-3-pyridazinone, the potassium carbonate powder of 0.6mmol porphyrize and DMSO5ml room temperature (25 ℃) stirred 0.5 hour.Add the O.5mmol DMSO solution 10ml of 2-Lv benzoxazole then, 25 ℃ were reacted 7 hours down.Reaction solution is neutralized with 5% dilute hydrochloric acid, use extracted with diethyl ether, saturated sodium bicarbonate solution washing organic phase, anhydrous magnesium sulfate drying.Organic phase uses column chromatography after being spin-dried for, and eluent is an ethyl acetate: sherwood oil obtains white solid, productive rate 54%
Embodiment 5:2,6-methyl 4-(3-trifluoromethyl)-3-pyridazinone
Add ethanol 5ml in the exsiccant reactor, contain the ethanolic soln solution of 1mmol sodium ethylate, add 4-(3-trifluoromethyl)-6-methyl-3-pyridazinone 1mmol behind the stirring 5min, be stirred to whole dissolvings.Add methyl iodide 1mmol, 15 ℃ were reacted 12 hours down.Reaction solution is spin-dried for, and resistates uses column chromatography, and eluent is an ethyl acetate: sherwood oil obtains white solid, productive rate 74%
Synthesized compound (I) (II) according to similar method, all compounds are through nuclear-magnetism, and ultimate analysis is proved conclusively.Part of compounds has been done infrared.Concrete outcome sees Table 1,2
Table 1 compound (I)
Physical properties characterize
| No. | R 1 | R 2 | R 3 | State (mp ℃) |
| 1 | m-CF 3 | CH 3 | CH 2COOC 2H | White powder (80-81) |
| 2 | m-CF 3 | CH 3 | CH 3 | White powder |
| 3 | m-CF 3 | CH 3 | CH 2CH＝CH 2 | Light yellow thick liquid |
| 4 | m-CF 3 | CH 3 | CH 2C 6H 5 | Light yellow thick liquid |
| 5 | m-CF 3 | CH 3 | C 2H 5 | Light yellow thick liquid |
| 6 | m-CF 3 | CH 3 | CH 2CH 2CH 3 | Light yellow thick liquid |
| 7 | m-CF 3 | CH 3 | CH 2CH 2(CH 3)CH 3 | Light yellow thick liquid |
| No. | R 1 | R 2 | R 3 | State (mp ℃) |
| 8 | m-CF 3 | CH 3 | CO 2C 2H 5 | Light yellow thick liquid |
| 9 | m-CF 3 | CH 3 | H | White powder (175-176) |
| 10 | m-OMe | CH 3 | H | White powder (150-152) |
Table 2 compound (II)
Physical properties characterize
Table 3 compound (I)
1HNMR composes data
| No. | 1HNMR(δ，CDCl 3) |
| 1 | 1.28-1.33(3H，t，J H＝7.2Hz)，2.41(3H，s)，4.25-4.28(2H，d，J H＝7.2Hz)， 4.91(2H，s)，7.29(1H，s)，7.53-7.59(1H，t，J H＝7.8Hz)，7.67-7.69(1H，d，J H＝7.8Hz)， 8.00-8.03(1H，d，J H＝8.4Hz)，8.041(1H，s) |
| No. | 1HNMR(δ，CDCl 3) |
| 2 | 2.39(3H，s)，3.83(3H，s)，7.25(1H，s)，7.54-7.58(1H，t，J H＝7.8Hz)， 7.66-7.68(1H，d，J H＝8.0Hz)，8.00-8.02(1H，d，J H＝8.0Hz)，8.03(1H，s) |
| 3 | 2.39(3H，s)，4.79-4.81(2H，d，J H＝6.0Hz)，5.24-5.31(2H，t，J H＝14.4Hz)， 5.99-6.05(1H，m)，7.24(1H，s)，7.52-7.56(1H，t，J H＝7.8Hz)， 7.64-7.66(1H，d，J H＝7.6Hz)，7.98-8.00(1H，d，J H＝7.6Hz)，8.03(1H，s) |
| 4 | 2.40(3H，s)，5.36(2H，s)，7.21(1H，s)，7.28-7.35(3H，m)，7.48-7.49(2H，m)， 7.52-7.56(1H，t，J H＝6.0Hz)，7.64-7.66(1H，d，J H＝8.0Hz)，7.99-7.80(2H，m) |
| 5 | 1.39-1.42(3H，t，J H＝7.2Hz)，2.40(3H，s)，4.23-4.28(2H，m)，7.22(1H，s)， 7.53-7.57(1H，t，J H＝7.8Hz)，7.65-7.67(1H，d，J H＝7.6Hz)， 7.99-8.01(1H，d，J H＝7.6Hz)，8.03(1H，s) |
| 6 | 0.96-1.00(3H，t，J H＝7.4Hz)，1.83-1.89(2H，m)，2.39(3H，s)， 4.14-4.17(2H，t，J H＝7.6Hz)，7.22(1H，s)，7.52-7.56(1H，t，J H＝7.8Hz)， 7.64-7.66(1H，d，J H＝7.6Hz)，7.99-8.01(1H，d，J H＝8.0Hz)，8.04(1H，s) |
| 7 | 0.97(3H，s)，0.98(3H，s)，1.64-1.75(3H，m)，2.39(3H，s)，4.19-4.23(2H，t，J H＝7.4Hz)， 7.21(1H，s)，7.53-7.56(1H，t，J H＝7.6Hz)，7.65-7.66(1H，d，J H＝7.6Hz)， 7.99-8.02(2H，m) |
| 8 | 1.44-1.48(3H，t，J H＝7.2Hz)，2.44(3H，s)，4.52-4.57(2H，m)，7.23(1H，s)， 7.55-7.59(1H，t，J H＝7.8Hz)，7.69-7.71(1H，d，J H＝8.0Hz)， 7.96-7.98(1H，d，J H＝8.0Hz)，7.99(1H，s) |
| 9 | 2.42(3H，s)，7.317(1H，s)，7.57-7.60(1H，t，J H＝7.8Hz)，7.68-7.70(1H，d，J H＝7.6Hz)， 8.02(1H，s)，8.09-8.11(1H，d，J H＝7.6Hz)，11.77(1H，s) |
| 10 | 2.38(3H，s)，3.85(3H，s)，6.94-6.99(2H，m)，7.35-7.40(3H，m)，11.21(1H，s) |
Table 4 compound (II)
1HNMR composes data
| No. | 1HNMR(δ，CDCl 3) |
| 11 | 2.53(3H，s)，7，37(1H，s)，7.38-7.46(2H，m)，7.58-7.65(2H，m)，7.72-7.75(1H，d，J H＝7.8Hz)， 7.83-7.86(1H，m)，8.04-8.07(1H，d，J H＝7.8Hz)，8.106(1H，s) |
| 12 | 2.53(3H，s)，7.37(1H，s)，7.39-7.43(1H，m)，7.61-7.64(2H，m)，7.73-7.77(2H，m) 8.03-8.06(1H，d，J H＝7.8Hz)，8.094(1H，s) |
| 13 | 2.516(6H，s)，7.22-7.24(1H，d，J H＝8.1Hz)，7.36(1H，s)，7.42(1H，s)， 7.57-7.63(1H，t，J H＝7.95Hz)，7.69-7.74(2H，m)，8.04-8.06(1H，d，J H＝8.1Hz)，8.10(1H，s) |
| 14 | 2.52(1H，s)，7.34(1H，s)，7.58-7.63(1H，t，J H＝7.8Hz)，7.72-7.75(1H，d，J H＝7.8Hz)， 7.82-7.84(1H，d，J H＝5.4Hz)，7.97-7.99((1H，d，J H＝7.8Hz)，8.022(1H，s)， 8.77-8.78(1H，d，J H＝5.4Hz) |
| 15 | 2.68(3H，s)，7.41(1H，s)，7.42-7.46(1H，t，d，，J H＝7.4Hz)，7.52-7.56(1H，t，d，，J H＝7.6Hz)， 7.62-7.66(1H，t，d，，J H＝8Hz)，7.75-7.77(1H，d，，J H＝7.6Hz)，7.91-7.93(1H，d，J H＝7.6Hz)， 8.05(2H，s)，8.16-8.18(1H，d，J H＝8Hz) |
| 16 | 2.705(3H，s)，7.45(1H，s)，7.65-7.69(1H，t，d，，J H＝8Hz)，7.78-7.80(1H，d，J H＝7.6Hz)， 8.05(2H，s)，8.23-8.25(1H，d，J H＝9.2Hz)，8.39-8.42(1H，m)8.87(1H，d，J H＝2.0Hz) |
Embodiment 6: the primary dcreening operation of weeding activity is measured
The little agar diffusion method of barnyard grass grass: add a filter paper in the beaker of the 50ml of covering one deck granulated glass sphere, add 5 milliliters of certain density test compound solution, 10 of the barnyard grass grass seeds that sowing shows money or valuables one carries unintentionally, under 25 ± 1 ℃, illumination 12 hours, under dark 12 hours the culture system, cultivate and measure plant height, root length, fresh weight and range estimation albefaction rate after 7 days.By compound the growth-inhibiting and the albefaction effect of barnyard grass grass are come the weeding activity of detection compound.
The little agar diffusion method of rape: add a filter paper in the beaker of the 50ml of covering one deck granulated glass sphere, add 5 milliliters of certain density test compound solution, 10 of the Semen Brassicae campestriss that sowing shows money or valuables one carries unintentionally, under 25 ± 1 ℃, illumination 12 hours, under dark 12 hours the culture system, cultivate to measure after 7 days to cultivate and measure plant height, root length, fresh weight and range estimation albefaction rate after 7 days.。By compound the growth-inhibiting and the albefaction effect of rape are come the weeding activity of detection compound.
Table 5 part of compounds (I) weeding activity (II)
Annotate: albefaction degree and rape plant height, the long inhibiting rate grade scale of root:
Below the A:85-100% B:70-84% C:55-69% D:40-54% E:40%
Annotate: albefaction degree and rape plant height, the long inhibiting rate grade scale of root:
Below the A:85-100% B:70-84% C:55-69% D:40-54% E:40%
A1：85-90％ A2：90-95％ A3：95-100％
Claims (4)
1. 4-substituted benzene radical pyridazine compound is characterized in that it is that general formula is the compound of (II):
Wherein,
R
1: haloalkyl;
R
2: alkyl;
R
4: benzoxazolyl, benzothiazolyl, pyrimidyl, the benzoxazolyl of replacement, benzothiazolyl, pyrimidyl;
Substituting group on benzoxazole ring, benzothiazole ring, the pyrimidine ring is alkyl, haloalkyl, halogenated alkoxy, halogen, cyano group or nitro, and substituting group quantity is 1～5;
Said alkyl is C
1～C
6Alkyl;
N=1 or 2.
2. compound according to claim 1 is characterized in that said R
1Be-m-CF
3, R
2Be 6-CH
3-,
R
4Be
3. the preparation method of compound according to claim 1 is characterized in that it is through following step:
(1) substituted acyl ethyl propionate and hydrazine hydrate mix, and its mol ratio is 1: 1～1: 2, adds a small amount of alcoholic solvent, and mixture was 0～90 ℃ of reaction 0.5～2 hour, and placement is spent the night, and obtains colourless tabular crystal, is 4,5-dihydro-6-replacement-3-pyridazinone;
(2) 4,5-dihydro-6-replacement-3-pyridazinone is dissolved in the solvent Glacial acetic acid, and dropping liquid bromine mol ratio is 1: 1～1: 3, drip off post-heating to 40～100 ℃, reflux to place after 5～60 minutes and spend the night, be the mixture of 6-replacement-3-pyridazinone and hydrogen bromide with the reaction solution suction filtration next day; 6-replacement-3-the pyridazinone that makes and the mixture of hydrogen bromide are dissolved in the solvent Glacial acetic acid, and adding the anhydrous sodium acetate mol ratio is 1: 1～1: 3; Reacted 0.5～2 hour mixture heating up to 40～110 ℃; Remove solvent under reduced pressure, resistates joins in the frozen water, suction filtration, and drying obtains white solid 6-replacement-3-pyridazinone;
(3) 6-replacement-3-pyridazinone is dissolved in the solvent anhydrous tetrahydro furan, 0～70 ℃ was reacted 2～7 hours with the substituted-phenyl magnesium bromide down; Reactant is through hydrolysis, washing, and drying is spin-dried for solvent after column chromatography for separation, and eluent is an ethyl acetate: sherwood oil obtains 4-(substituted-phenyl)-6-replacement-3-pyridazinone and 4,5-dihydro-4-(substituted-phenyl)-6-replacement-3-pyridazinone;
(4) 4-(substituted-phenyl)-6-replacement-3-pyridazinone and potassium carbonate powder and 2-chlorine are replaced benzoxazole or 2-chlorine replace benzothiazole or 2-chlorine substituted pyrimidines with mol ratio 1: 1～3: 1～2 at solvent N, react in the N-dimethyl sulfoxide (DMSO); Temperature of reaction is 0～70 ℃, and the reaction times is 1～48 hour; Reaction afterreaction liquid uses column chromatography after organic phase is spin-dried for through neutralization, extraction, drying, obtains solid, for 3-substituted oxy-4-(substituted-phenyl)-6-replaces pyridazine;
4. the described application of compound of claim 1 is characterized in that, as bleaching herbicide, can prevent and kill off annual gramineous weed and broadleaf weeds.
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| WO2019148850A1 (en) * | 2018-02-02 | 2019-08-08 | 青岛清原化合物有限公司 | Pyridine ring-substituted pyridazinol compound and derivatives thereof, preparation method, herbicidal composition, and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0450359A1 (en) * | 1990-04-05 | 1991-10-09 | Sandoz Ltd. | Herbicidal agent |
| US5623072A (en) * | 1994-10-11 | 1997-04-22 | Monsanto Company | 3-phenylpyridazines, herbicidal compositions and uses thereof |
| WO1999052878A1 (en) * | 1998-04-09 | 1999-10-21 | Bayer Aktiengesellschaft | Substituted phenyl pyridazinones |
| CN1236301A (en) * | 1997-02-17 | 1999-11-24 | 住友化学工业株式会社 | Herbicidal composition |
| JP2000178272A (en) * | 1998-10-08 | 2000-06-27 | Otsuka Chem Co Ltd | Benzylpiperidine compound, its production and inseticide for agriculture and horticulture |
-
2005
- 2005-03-17 CN CN200710084270A patent/CN101041639B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0450359A1 (en) * | 1990-04-05 | 1991-10-09 | Sandoz Ltd. | Herbicidal agent |
| US5623072A (en) * | 1994-10-11 | 1997-04-22 | Monsanto Company | 3-phenylpyridazines, herbicidal compositions and uses thereof |
| CN1236301A (en) * | 1997-02-17 | 1999-11-24 | 住友化学工业株式会社 | Herbicidal composition |
| WO1999052878A1 (en) * | 1998-04-09 | 1999-10-21 | Bayer Aktiengesellschaft | Substituted phenyl pyridazinones |
| JP2000178272A (en) * | 1998-10-08 | 2000-06-27 | Otsuka Chem Co Ltd | Benzylpiperidine compound, its production and inseticide for agriculture and horticulture |
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| CN101041639A (en) | 2007-09-26 |
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