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CN1962642A - Trifluoromethylphenylpyridazine derivative and its preparation method - Google Patents

Trifluoromethylphenylpyridazine derivative and its preparation method Download PDF

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CN1962642A
CN1962642A CN 200610129467 CN200610129467A CN1962642A CN 1962642 A CN1962642 A CN 1962642A CN 200610129467 CN200610129467 CN 200610129467 CN 200610129467 A CN200610129467 A CN 200610129467A CN 1962642 A CN1962642 A CN 1962642A
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arh
methyl
trifluoromethylphenyl
phenyl
benzyl
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邹小毛
杨华铮
许寒
刘斌
胡绪红
朱有全
胡方中
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Nankai University
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Nankai University
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Abstract

具有除草活性的三氟甲基苯基哒嗪类衍生物及制备方法。化合物(I)(II)的通式如下。该化合物具有较高的除草活性。它可有效防除禾本科杂草及阔叶杂草。其中，R1：H、烷基、苯基、取代苯基、烷氧基、苯基烷氧基、羟基烷基、烷氧烷基、卤代烷基、卤代烷氧基、硝基、氰基、烷基胺基、二烷基胺基、乙酰氨基等；R2：H、烷基、苯基、取代苯基、烷氧基、苯基烷氧基、羟基烷基、烷氧烷基、卤代烷基、卤代烷氧基、硝基、氰基、烷基胺基、二烷基胺基、乙酰氨基等；R3：H、苄基、取代苄基、烷基、羟基烷基、烷氧烷基、卤代烷基、烯基、卤代烯基等；R4：苄基、取代苄基、苯基、取代苯基等；X：O、NH、S等。

Figure 200610129467

Trifluoromethylphenylpyridazine derivatives with herbicidal activity and preparation method. The general formula of compound (I)(II) is as follows. The compound has high herbicidal activity. It can effectively control grass weeds and broadleaf weeds. Among them, R 1 : H, alkyl, phenyl, substituted phenyl, alkoxy, phenylalkoxy, hydroxyalkyl, alkoxyalkyl, haloalkyl, haloalkoxy, nitro, cyano, alkane Amino, dialkylamino, acetamido, etc.; R 2 : H, alkyl, phenyl, substituted phenyl, alkoxy, phenylalkoxy, hydroxyalkyl, alkoxyalkyl, haloalkyl , haloalkoxy, nitro, cyano, alkylamino, dialkylamino, acetamido, etc.; R 3 : H, benzyl, substituted benzyl, alkyl, hydroxyalkyl, alkoxyalkyl, Haloalkyl, alkenyl, haloalkenyl, etc.; R 4 : benzyl, substituted benzyl, phenyl, substituted phenyl, etc.; X: O, NH, S, etc.

Figure 200610129467

Description

Trifluoromethyl pyridazine class derivative and preparation method with weeding activity
[technical field]: the present invention relates to the technical field of weedicide and preparation thereof, the preparation of particularly a kind of 4-(3-trifluoromethyl) pyridazine compound, compound and the application in weeding.
[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.
[summary of the invention]: the objective of the invention is to solve in the presence of bleaching herbicide; carotenoid in the chloroplast(id) can not be brought into play provide protection and have degraded chlorophyll and destroy the problem of photosynthetic film, and a kind of trifluoromethyl pyridazine class derivative and preparation method with weeding activity is provided.
The general formula of The compounds of this invention is (I) or (II):
Wherein,
R 1: H, alkyl, alkoxyl group, phenyl, optional phenyl, phenyl alkoxyl group, hydroxyalkyl, alkoxyalkyl, haloalkyl, halo institute oxygen base, alkylthio, thiazolinyl, haloalkenyl group, carboxyl, alkoxy carbonyl, alkyl amine group carbonyl, dialkyl amino carbonyl, aminocarboxyl, halogen, nitro, cyano group, alkyl amine group, dialkyl amino, kharophen, the COR that replaces 5, NR 6R 7, 3～6 yuan of carbocyclic ring or heterocycles;
R 2: H, alkyl, alkoxyl group, phenyl, optional phenyl, phenyl alkoxyl group, hydroxyalkyl, alkoxyalkyl, halo institute base, halogenated alkoxy, alkylthio, thiazolinyl, haloalkenyl group, carboxyl, alkoxy carbonyl, alkyl amine group carbonyl, dialkyl amino carbonyl, aminocarboxyl, halogen, nitro, cyano group, alkyl amine group, dialkyl amino, kharophen, the COR that replaces 5, NR 6R 7, 3～6 yuan of carbocyclic ring or heterocycles;
R 3: benzyl, the optional benzyl that replaces, phenyl, optional phenyl, H, alkyl, hydroxyalkyl, alkoxyalkyl, haloalkyl, thiazolinyl, haloalkenyl group, ester group, alkoxy carbonyl, alkyl amine group carbonyl, dialkyl amino carbonyl, aminocarboxyl, the COR that replaces 5, SO 2R 5, 3～6 yuan of carbocyclic ring or heterocycles;
R 4: benzyl, the optional benzyl that replaces, phenyl, the optional phenyl that replaces, phenylalkyl, optional phenylalkyl, furyl, benzoxazolyl, benzothiazolyl, pyrimidyl, pyrazolyl, pyridazinyl, pyridyl, H, alkyl, hydroxyalkyl, alkoxyalkyl, haloalkyl, thiazolinyl, haloalkenyl group, ester group, benzyl, the COR that replaces 5, SO 2R 5, 3～6 yuan of carbocyclic ring or heterocycles, optional furyl, benzoxazolyl, benzothiazolyl, pyrimidyl, pyrazolyl, pyridazine, the pyridyl that replaces;
X:O, S or N-R 8
R 5: H, alkyl, haloalkyl;
R 6R 7: H, alkyl, R 6, R 7Can be identical, also can be different;
R 8: H, alkyl;
Substituting group on phenyl ring and the heterocycle is alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, alkylthio, halogenated alkylthio, cyano group, nitro, and substituting group quantity is 1～5.
Said alkyl is C 1～C 6Alkyl.
Said R 1Be methyl, trifluoromethyl, chlorine, bromine, methoxyl group, oxyethyl group, methylamino-, dimethylamino, phenyl, m-trifluoromethylphenyl, m-methoxyphenyl, a bromophenyl, an aminomethyl phenyl, o-trifluoromethyl phenyl, o-methoxyphenyl, o-bromophenyl, o-methyl-phenyl-, p-trifluoromethyl phenyl, p-methoxyphenyl, to bromophenyl, p-methylphenyl;
R 2Be hydrogen, methyl, trifluoromethyl, chlorine, bromine, methoxyl group, oxyethyl group, methylamino-, dimethylamino, phenyl, m-trifluoromethylphenyl, m-methoxyphenyl, a bromophenyl, an aminomethyl phenyl, o-trifluoromethyl phenyl, o-methoxyphenyl, o-bromophenyl, o-methyl-phenyl-, p-trifluoromethyl phenyl, p-methoxyphenyl, to bromophenyl, p-methylphenyl;
R 3Be to nitrobenzyl, a nitrobenzyl, adjacent nitrobenzyl, adjacent luorobenzyl, a luorobenzyl, to luorobenzyl, 2,4-difluorobenzyl, 2,6-difluorobenzyl, 2-cyano group benzyl, 3-cyano group benzyl, 4-cyano group benzyl, 2-benzyl chloride base, 3-benzyl chloride base, 4-benzyl chloride base, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-methoxy-benzyl, 3-methoxy-benzyl, 4-methoxy-benzyl, 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl, benzyl, 4-tertiary butyl benzyl, 2-chloro-5-pyridine benzyl, 2-methoxycarbonyl-5-pyridine benzyl;
R 4It is adjacent luorobenzyl, between luorobenzyl, to luorobenzyl, 2, the 4-difluorobenzyl, 2, the 6-difluorobenzyl, 2-cyano group benzyl, 3-cyano group benzyl, 4-cyano group benzyl, 2-benzyl chloride base, 3-benzyl chloride base, 4-benzyl chloride base, the 2-bromobenzyl, the 3-bromobenzyl, the 4-bromobenzyl, the 2-methoxy-benzyl, the 3-methoxy-benzyl, the 4-methoxy-benzyl, the 2-methyl-benzyl, the 3-methyl-benzyl, the 4-methyl-benzyl, 3, the 5-dimethyl benzyl, the 2-trifluoromethyl benzyl, the 3-trifluoromethyl benzyl, the 4-trifluoromethyl benzyl, 2, the 6-dichloro benzyl, 2, the 4-dichloro benzyl, 4-dimethylamino benzyl, the 3-aminobenzyl, styroyl, α methyl-benzyl [C 6H 5CH (CH 3)], 2-thiophene phenol ethyl [2-thiophene-CH 2CH 2], 2-furans benzyl [2-furan-CH 2], α methyl 4-benzyl chloride base [4-ClC 6H 4CH (CH 3)], α methyl 4-luorobenzyl [4-FC 6H 4CH (CH 3)].
The compounds of this invention (I) or synthetic route (II) are as follows:
Concrete preparation method, finish through following steps:
(1) trimethyl orthoformate mixes with martonite, and wherein mol ratio is 1: 0.5～1, adds alcoholic solvent and inhales the vitriol oil, and mixture is at 0.5～48 hour post neutralization of 0～90 ℃ of reaction, and underpressure distillation obtains product 1-bromo-2,2-Propanal dimethyl acetal;
(2) will go up the 1-bromo-2 that obtains in the step, the diisopropyl ethyl amine tosilate Hybrid Heating to 40 of 2-Propanal dimethyl acetal and catalytic amount～240 ℃, distillation obtains the mixture of 3-bromo-2-methoxyl group propylene and 2-methoxyl group allyl bromide 98;
(3) sodium hydride and solvent N, dinethylformamide mixes the DMF solution that the back adds the m-trifluoromethyl Phenylacetic acid ethylester, stir after 0.5～4 hour to add and go up the 3-bromo-2-methoxyl group propylene that obtains in the step and the DMF solution of 2-methoxyl group allyl bromide 98, mol ratio is 1～2: 1: 1～4,0～120 ℃ was reacted 1～48 hour, the acidifying of reaction solution cooling back, extraction, drying obtain the crude product of 4-oxo-2-(3-trifluoromethyl)-Valeric acid ethylester after organic phase is spin-dried for; The crude product of 4-oxo-2-(3-trifluoromethyl)-Valeric acid ethylester is mixed with hydrazine hydrate, mol ratio is 1: 1～2, add alcoholic solvent, reflux 0.5～24 hour, mixture is poured in the water, suction filtration obtains yellow solid 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone;
(4) will go up the 6-methyl-4-(3-trifluoromethyl)-4 that obtains in the step, 5-dihydro-3 (2H) pyridazinone mixes in dimethyl sulfoxide (DMSO) with the Anhydrous potassium carbonate powder, mol ratio is 1: 1～2, stirred 0.5～24 hour in the time of 0～90 ℃, reaction solution is poured in the water into extraction, drying, obtain yellow solid after being spin-dried for, be 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone;
(5) with sodium hydride and anhydrous N, dinethylformamide mixes, 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone that obtains in step in the adding, mol ratio is 1～2: 1, is stirred to whole dissolvings, adds the halides of 1～2 times of amount, 0～110 ℃ was reacted 1～48 hour down, reaction solution is spin-dried for, and resistates uses column chromatography, and obtaining solid or liquid is N-replacement-6-methyl-4-(3-trifluoromethyl)-3 (2H)-pyridazinones;
(6) will go up 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone that obtains in the step mixes with phosphorus oxychloride, stirred 0.5～24 hour in the time of 0～100 ℃, resistates was poured in the water after phosphorus oxychloride was steamed and removed, suction filtration obtains white solid, is 3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine;
(7) with sodium hydride and anhydrous N, dinethylformamide mixes, add (replacement) benzylalcohol, mol ratio is 1～2: 1, is stirred to whole dissolvings, adds 3-chloro-6-methyl-4-(3-the trifluoromethyl)-pyridazine that obtains in the step of going up of 1～2 times of amount, 0～110 ℃ was reacted 1～48 hour down, reaction solution is poured in the water, collects the solid that obtains, and is 3-(replacement) benzyloxy-6-methyl-4-(3-trifluoromethyl)-pyridazine;
(8) will go up 3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine of obtaining of step mixes with (replacement) benzylamine, 100～250 ℃ of reactions 1～72 hour, column chromatography for separation obtained product 3-(replacement) benzamido group-6-methyl-4-(3-trifluoromethyl)-pyridazine.
Described application of compound as bleaching herbicide, can be prevented and kill off annual gramineous weed and broadleaf weeds.
Advantage of the present invention and effect: the active aspect of the weeding activity of the 4-that relates in this patent (3-trifluoromethyl) pyridazine compound and albefaction is enhanced, and especially performance is more outstanding on to the selectivity of crop.Compound of the present invention has very high weeding activity to broadleaf weed, and crop is shown good selectivity, can the direct dispenser in farmland under 150 gram/hectare dosage.
[embodiment]:
Embodiment 1:
One, the 1-bromo-2,2-Propanal dimethyl acetal synthetic
Add 19.6g (185mol) trimethyl orthoformate in the 100mL round-bottomed bottle, 2mL dehydrated alcohol, the vitriol oil of 16.0g (117mmol) martonite and 0.06g98%.Mixture is used N behind stirring at room 24h, the accelerine neutralization.Remove methyl alcohol and methyl-formiate under reduced pressure, then with product 1-bromo-2, (58-60 ℃, 40mmHg) decompression steams productive rate 79% to the 2-Propanal dimethyl acetal.
Two, 3-bromo-2-methoxyl group propylene and 2-methoxyl group allyl bromide 98 is synthetic
25g (137mmol) 1-bromo-2,2-Propanal dimethyl acetal and 0.4g diisopropyl ethyl amine tosilate Hybrid Heating steam methyl alcohol to 150-190 ℃ (the outer bath) with fractionation plant.After methyl alcohol steamed, temperature rose greater than 130 ℃ rapidly, uses common water distilling apparatus instead and steams product, collects product 15.1g, is the mixture of 3-bromo-2-methoxyl group propylene and 2-methoxyl group allyl bromide 98.
Three, 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone is synthetic
Add 3.6g80%NaH (120mmol) and the anhydrous N of 20mL in the 250mL there-necked flask, dinethylformamide, the back that stirs is cooled to 20 ℃ with ice-water bath with reaction solution, under this temperature, slowly drip the DMF solution of 23.2g m-trifluoromethyl Phenylacetic acid ethylester by dropping funnel, stir to clarify.Reaction solution is cooled to 10 ℃, drips the 3-bromo-2-methoxyl group propylene of 19.15g (120mmol) and the DMF solution of 2-methoxyl group allyl bromide 98, the back room temperature reaction 1h that finishes is heated to 80 ℃, reaction 20h.With the reaction solution cooling, drip dilute hydrochloric acid to PH＜3, (3 * 75mL) extract, and organic phase washes with water three times, and anhydrous sodium sulfate drying reduces pressure down solvent to be steamed and removes the crude product that obtains 4-oxo-2-(3-trifluoromethyl)-Valeric acid ethylester with methylene dichloride.The crude product of 4-oxo-2-(3-trifluoromethyl)-Valeric acid ethylester is added in the 35 mL ethanol, and the ice bath cooling adds the hydrazine hydrate of 5.9g85%, reflux 3h down.Reaction mixture is slowly poured in the frozen water, obtain yellow solid, suction filtration is collected solid and washing, drying, obtain 6-methyl-4-(3-trifluoromethyl)-4, the mixture of 5-dihydro-3 (2H) pyridazinone and 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone.With mixture with dmso solution after, add equimolar Anhydrous potassium carbonate powder, stirring at room 24 hours reacts completely.Reaction solution is poured in the water, uses extracted with diethyl ether, and the organic phase drying is spin-dried for, through column chromatography to 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone.
Four, 2-benzyl-6-methyl-4-(3-trifluoromethyl)-3 (2H)-pyridazinones
Add 80%NaH powder 0.045g (1.5mmol) and anhydrous DMF solution 20mL in the 50mL round-bottomed bottle, the back that stirs adds 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone 0.25g (1mmol), stirring at room 0.5h.Reaction solution is cooled to 10 ℃, adds benzyl chlorine 0.13g (1mmol), 10 ℃ are stirred 1h down.Reaction solution is poured in the 30mL water, and (3 * 20mL) extractions, organic phase washes with water until the DMF in the organic phase is removed after merging with methylene dichloride.Organic phase anhydrous magnesium sulfate drying, decompression steam solvent down and remove, and resistates uses column chromatography and obtains 2-benzyl-6-methyl-4-(3-trifluoromethyl)-3 (2H)-pyridazinone 0.26g, productive rate 75%.
Synthesized compound (I) according to similar method, all compounds are through nuclear-magnetism, and infrared, ultimate analysis is proved conclusively.The physical parameter and the spectrum data of part of compounds the results are shown in Table 1,2.
Five, 3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine
Add 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone 2g in the 50ml round-bottomed bottle, phosphorus oxychloride 40ml, refluxed 2 hours, after the cooling phosphorus oxychloride decompression is steamed, resistates is poured in the water, in the alkali and back suction filtration obtains white solid, is 3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine.
Six, 3-benzyloxy-6-methyl-4-(3-trifluoromethyl)-pyridazine
Add 80%NaH powder 0.03g (1.0mol) and anhydrous DMF solution 20mL in the 50mL round-bottomed bottle, back adding benzylalcohol 0.06g (0.55mmol) stirs, stirring at room 0.5h, add 3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine 0.14g (0.5mol), be warming up to 90 ℃ of reaction 1h.The cooling back adds 20mL water in reaction solution, the adularescent solid is separated out, with the solid suction filtration, drying obtains white powder, and it is dissolved after-filtration with methylene dichloride, collect filtrate, obtain 3-benzyloxy-6-methyl-4-(3-trifluoromethyl)-pyridazine 0.14g after being spin-dried for, productive rate 81.4%.
Seven, 3-benzamido group-6-methyl-4-(3-trifluoromethyl)-pyridazine
Add 3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine 0.14g (0.5mol) in the 5mL heart bottle, benzylamine 0.27g, be warming up to 190 ℃ of reaction 20h, cooling back with a small amount of methylene dichloride with the reaction solution stripping, directly use column chromatography and obtain 3-benzamido group-6-methyl-4-(3-trifluoromethyl)-pyridazine 0.10g, productive rate 58.3%.
Synthesized compound (I), compound (II) according to similar method, all compounds are through nuclear-magnetism, and infrared, ultimate analysis is proved conclusively.The physical parameter and the spectrum data of part of compounds the results are shown in Table 1,2.
The physical properties of table 1 compound (I) characterizes
Compound R 1 R 2 R 3 Outward appearance (fusing point/℃)
I-1 I-2 CH 3 CH 3 H H 4-NO 2C 6H 4CH 2 2-FC 6H 4CH 2 Yellow solid (127-128) brown thick liquid
I-3 I-4 I-5 I-6 I-7 I-8 I-9 I-10 I-11 I-12 I-13 I-14 I-15 I-16 I-17 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H H H H H 2，4-F 2C 6H 3CH 22-CNC 6H 4CH 24-ClC 6H 4CH 24-CH 3C 6H 4CH 24-(tert-Bu)C 6H 4CH 24-CNC 6H 4CH 23-ClC 6H 4CH 22，6-F 2C 6H 3CH 2C 6H 5CH 22-Cl-5-pyridine-CH 22-COOCH 3-5-pyridine-CH 22-ClC 6H 4CH 22-CH 3C 6H 4CH 24-CH 3OC 6H 4CH 24-BrC 6H 4CH 2 The yellow thick liquid white solid (103-104) of the yellow thick liquid of the yellow thick liquid of the yellow yellow thick liquid yellow solid of thick liquid (78-80) the light yellow thick liquid of the yellow thick liquid yellow thick liquid of the yellow light yellow thick liquid white solid of thick liquid (86-88) yellow solid (74-76) of yellow thick liquid
The physical properties of table 2 compound (II) characterizes
Compound R 1 R 2 X R 3 Outward appearance Fusing point/℃
II-1 II-2 II-3 II-4 II-5 II-6 II-7 II-8 II-9 II-10 II-11 II-12 II-13 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H H H O O O O O O O O O O O O O 4-CH 3OC 6H 4CH 2 C 6H 5CH 2 2-CH 3OC 6H 4CH 2 3-CH 3OC 6H 4CH 2 2-CH 3C 6H 4CH 2 3-CH 3C 6H 4CH 2 4-BrC 6H 4CH 2 3，5-(CH 3) 2C 6H 3CH 2 2-ClC 6H 4CH 2 3-ClC 6H 4CH 2 4-ClC 6H 4CH 2 2-FC 6H 4CH 2 3-FC 6H 4CH 2 The light brown solid of white solid white solid white solid white solid white solid white solid white solid white solid white solid white solid yellow solid light yellow solid 108-109 79-80 94-96 125-126 60-62 83-85 75-77 100-102 99-100 89-90 73-75 120-122 92-93
II-14 II-15 II-16 II-17 II-18 II-19 II-20 II-21 III-1 III-2 III-3 III-4 III-5 III-6 III-7 III-8 III-9 III-10 III-11 III-12 III-13 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H H H H H H H H H H H O O O 0 O O O O NH NH NH NH NH NH NH NH NH NH NH NH NH 2-CF 3C 6H 4CH 24-CH 3C 6H 4CH 22，6-Cl 2C 6H 3CH 22，4-Cl 2C 6H 3CH 22-BrC 6H 4CH 23-BrC 6H 4CH 24-FC 6H 4CH 24-(CH 3) 2NC 6H 4CH 2C 6H 5CH 22-FC 6H 4CH 22-ClC 6H 4CH 24-FC 6H 4CH 24-CH 3OC 6H 4CH 2C 6H 5CH 2CH 23-NH 2C 6H 4CH 2C 6H 5CH(CH 3) 2-thiophene-CH 2CH 22-furan-CH 24-ClC 6H 4CH(CH 3) 4-FC 6H 4CH(CH 3) 4-CH 3C 6H 4CH 2 The light brown solid white solid of white solid white solid white solid white solid white solid white solid white solid yellow solid light yellow solid light yellow solid light yellow solid light yellow solid light yellow solid white solid brown thick liquid white solid light brown solid brown thick liquid light yellow solid 100-102 120-121 101-103 110-112 103-105 94-95 84-86 126-128 162-164 130-131 99-101 88-90 83-85 124-126 178-180 95-97 118-120 101-103 95-97
Table 2 compound (I) (II) 1The HNMR spectrum data
No (CDCl 3) 1H NMR
I-1 2.42(s，3H，CH 3)，5.43(s，2H，CH 2)，7.26(s，1H，pyridazinone)， 7.53-7.69(m，4H，4ArH)，7.97-8.00(m，2H，2ArH)，8.18-8.20(d，2H， J H＝8.4Hz，2ArH)
I-2 2.40(s，3H，CH 3)，5.45(s，2H，CH 2)，7.03-7.11(m，2H， ArH+pyridazinone)，7.23-7.38(m，3H，3ArH)，7.52-7.57(t，1H，J H＝
7.8Hz，ArH)，7.65-7.68(d，1H，J H＝7.8Hz，ArH)，8.01(s，1H，ArH)， 8.01-8.03(d，1H，J H＝6.9Hz，ArH)
I-3* 2.40(s，3H，CH 3)，5.46(s，2H，CH 2)，7.10-7.12(d，1H，J H＝8.4Hz，ArH)， 7.17-7.19(m，1H，ArH)，7.28(s，1H，pyridazinone)，7.41(m，1H，ArH)， 7.54-7.58(t，1H，J H＝8.2Hz，ArH)，7.66-7.68(d，1H，J H＝7.6Hz，ArH)， 8.02(m，2H，2ArH)
I-4* 2.41(s，3H，CH 3)，5.60(s，2H，CH 2)，7.27(s，1H，pyridazinone)， 7.37-7.44(m，2H，2ArH)，7.52-7.58(m，2H，2ArH)，7.66-7.70(m，2H， 2ArH)，8.00-8.02(m，2H，2ArH)
I-5* 2.39(s，3H，CH 3)，5.31(s，2H，CH 2)，7.22(s，1H，pyridazinone)， 7.28-7.30(d，2H，J H＝8.4Hz，2ArH)，7.42-7.44(d，2H，J H＝8.0Hz，2ArH)， 7.52-7.56(t，1H，J H＝8.0Hz，ArH)，7.65-7.68(d，1H，J H＝8.0Hz，ArH)， 7.97-7.98(d，1H，J H＝6.8Hz，ArH)，7.98(s，1H，ArH)
I-6* 2.32-2.48(m，6H，2CH 3)，5.32(s，2H，CH 2)，7.13-7.20(m，3H， 2ArH+pyridazinone)，7.24(s，1H，ArH)，7.38-7.40(d，1H，J H＝8.0Hz， ArH)，7.52-7.57(m，1H，ArH)，7.55-7.66(m，1H，ArH)，8.00(m，2H， ArH)
I-7* 1.29(s，9H，3CH 3)，2.40(s，3H，CH 3)，5.33(s，2H，CH 2)，7.20(s，1H， pyridazinone)，7.33-7.35(d，2H，J H＝8.0Hz，2ArH)，7.42-7.44(d，2H， J H＝8.0Hz，2ArH)，7.52-7.56(t，1H，J H＝8.0Hz，ArH)，7.64-7.66(d，1H， J H＝7.6Hz，ArH)，7.99(m，2H，2ArH)
I-8* 2.41(s，3 H， CH 3)，5.38(s，2H，CH 2)，7.25(s，1H，pyridazinone)， 7.53-7.67(m，6H，6ArH)，7.96-7.99(d，1H，J H＝10.8Hz，ArH)，7.99(s， 1H，ArH)
I-9* 2.41(s，3H，CH 3)，5.31(s，2H，CH 2)，7.23(s，1H，pyridazinone)， 7.35-7.37(t，1H，J H＝4.0Hz，ArH)，7.44(s，1H，ArH)，7.53-7.57(t， 1H，J H＝8.0Hz，ArH)，7.65-7.67(d，1H，J H＝8.0Hz，ArH)，7.99(m，2H， 2ArH)
I-10 2.27(s，3H，CH 3)，5.40(s，2H，CH 2)，7.23(s，1H，pyridazinone)， 6.80-6.85(m，2H，ArH)，7.13(s，1H，ArH)，7.19(s，1H，ArH)，7.44-7.50
(t，1H，J H＝7.8Hz，ArH)，7.57-7.60(d，1H，J H＝7.8Hz，ArH)，7.92(s， 1H，ArH)，7.94-7.96(d，1H，J H＝7.8Hz，ArH)
I-11* 2.40(s，3H，CH 3)，5.36 (s，2H，CH 2)，7.21(s，1H， pyridazinone)，7.28-7.35(m，3H，3ArH)，7.48-7.49(m，2H，ArH)， 7.52-7.56(t，1H，J H＝6.0Hz，ArH)，7.64-7.66(d，1H，J H＝8.0Hz，ArH)， 7.99-7.80(m，2H，2ArH)
I-12 2.40(s，3H，CH 3)，5.33(s，2H，CH 2)，7.23(s，1H，pyridazinone)， 7.28-7.31(d，1H，J H＝8.1Hz，ArH)，7.54-7.58(t，1H，J H＝7.8Hz，ArH)， 7.67-7.69(d，1H，J H＝7.8Hz，ArH)，7.83-7.86(m，1H，ArH)，7.96-7.98 (m，2H，2ArH)，8.53-8.54(d，1H，J H＝2.4Hz，ArH)
I-13 2.44(s，3H，CH 3，3.93(s，3H，CH 3，5.56(s，2H，CH 2)，7.31(s，1H， pyridazinone)，7.36-7.39(d，1H，J H＝8.4Hz，ArH)，7.52-7.58(t，1H， J H＝7.8Hz，ArH)，7.66-7.68(d，1H，J H＝7.5Hz，ArH)，7.99-8.03(m，2H， 2ArH)，8.24-8.27(m，1H，ArH)，9.16-9.17(m，1H，ArH)
I-14 2.41(s，3H，CH 3)，5.12(s，2H，CH 2)，7.10-7.13(m，1H，ArH)，7.17-7.25 (m，2H，2ArH)，7.29(s，1H，pyridazinone)，7.38-7.41(m，1H，ArH)， 7.53-7.58(t，1H，J H＝8.1Hz，ArH)，7.66-7.69(d，1H，J H＝7.8Hz，ArH)， 8.03-8.05(m，2H，2ArH)
I-15 2.39(s，3H，CH 3)，2.48(s，3H，CH 3)，5.40(s，2H，CH 2)，7.13-7.26(m， 5H，4ArH+pyridazinone)，7.52-7.58(t，1H，J H＝8.1Hz，ArH)，7.65-7.68 (d，1H，J H＝7.8Hz，ArH)，8.01-8.03(m，2H，2ArH)
I-16 2.40(s，3H，CH 3)，3.78(s，3H，CH 3)，5.30(s，2H，CH 2)，6.84-6.87(m， 2H，2ArH)，7.20(s，1H，pyridazinone)，7.44-7.67(m，4H，4ArH)， 7.98-7.99(m，2H，2ArH)
I-17 2.40(s，3H，CH 3)，5.30(s，2H，CH 2)，7.22(s，1H，pyridazinone)， 7.36-7.47(m，4H，4ArH)，7.52-7.58(t，1H，J H＝8.1Hz，ArH)，7.65-7.68 (d，1H，J H＝7.8Hz，ArH)，7.97-7.99(m，2H，2ArH)
II-1 2.68(s，3H，CH 2，3.80(s，3H，O-CH 3)，5.58(s，2H，CH 2)，6.87-6.90 (d，2H，J H＝8.7Hz，2ArH)，7.28(s，1H，ArH)，7.38-7.41(d，2H，J H＝8.7Hz， 2ArH)，7.53-7.58(t，1H，J H＝7.8Hz，ArH)，7.66-7.69(d，1H，J H＝7.8Hz，
ArH)，7.78-7.81(d，1H，J H＝8.1Hz，ArH)，7.92(s，1H，ArH)
II-2 2.69(s，3H，CH 3)，5.64(s，2H，CH 2)，7.28-7.39(m，4H，4ArH)，7.44-7.46 (d，2H，J H＝6.6Hz，2ArH)，7.55-7.60(t，1H，J H＝7.8Hz，ArH)，7.68-7.70 (d，1H，J H＝7.5Hz，ArH)，7.80-7.83(d，1H，J H＝7.8Hz，ArH)，7.96(s， 1H，ArH)
II-3 2.69(s，3H，CH 3)，3.86(s，3H，O-CH 3)，5.66(s，2H，CH 2)，6.90-6.95 (m，2H，2ArH)，7.27-7.34(m，2H，2ArH)，7.39-7.42(d，1H，J H＝7.2Hz， ArH)，7.52-7.58(t，1H，J H＝7.6Hz，ArH)，7.65-7.68(d，1H，J H＝7.6Hz， ArH)，7.81-7.83(d，1H，J H＝7.5Hz，ArH)，8.00(s，1H，ArH)
II-4* 2.69(s，3H，CH 3)，3.77(s，3H，O-CH 3)，5.61(s，2H，CH 2)，6.83-6.85 (d，1H，J H＝8.0Hz，ArH)，6.95(s，1H，ArH)，7.01-7.03(d，1H，J H＝7.6Hz， ArH)，7.24-7.30(m，2H，2ArH)，7.55-7.59(t，1H，J H＝7.8Hz，ArH)， 6.67-6.69(d，1H，J H＝7.6Hz，ArH)，7.82-7.84(d，1H，J H＝8.0Hz，ArH)， 7.93(s，1H，ArH)
II-5* 2.36(s，3H，CH 3)，2.69(s，3H，CH 3)，5.64(s，2H，CH 2)，7.15-7.26(m， 3H，3ArH)，7.29(s，1H，ArH)，7.42-7.44(d，1H，J H＝7.2Hz，ArH)， 7.54-7.58(t，1H，J H＝7.8Hz，ArH)，7.67-7.69(d， 1H，J H＝7.6Hz，ArH)， 7.78-7.80(d，1H，J H＝7.6Hz，ArH)，7.92(s，1H，ArH)
II-6* 2.34(s，3H，CH 3)，2.69(s，3H，CH 3)，5.60(s，2H，CH 2)，7.11-7.13(m， 1H，ArH)，7.23-7.26(m，3H，3ArH)，7.29(s，1H，ArH)，7.55-7.59(t， 1H，J H＝7.8Hz，ArH)，7.67-7.69(d，1H，J H＝7.6Hz，ArH)，7.80-7.82((d， 1H，J H＝8.0Hz，ArH)，7.97(s，1H，ArH)
II-7* 2.68(s，3H，CH 3)，5.57(s，2H，CH 2)，7.30-7.32(m，3H，3ArH)，7.46-7.48 (d，1H，J H＝8.0Hz，ArH)，7.56-7.60(t，1H，J H＝7.8Hz，ArH)，7.69-7.71 (d，1H，J H＝7.6Hz，ArH)，7.78-7.79(d，1H，J H＝7.6Hz，ArH)，7.92(s， 1H，ArH)
II-8* 2.30(s，6H，2CH 3)，2.69(s，3H，CH 3)，5.56(s，2H，CH 2)，6.94(s，1H， ArH)，7.05(s，1H，ArH)，7.29(s，1H，ArH)，7.55-7.59(t，1H，J H＝7.8Hz， ArH)，7.67-7.69(d，1H，J H＝7.6Hz，ArH)，7.79-7.81(d，1H，J H＝7.6Hz， ArH)，7.99(s，1H，ArH)
II-9* 2.70(s，3H，CH 3)，5.71(s，2H，CH 2)，7.21-7.28(m，2H，2ArH)，7.31 (s，1H，ArH)，7.39-7.41(d，1H，J H＝7.6Hz，ArH)，7.49-7.51(d，1H，J H＝7.6Hz，ArH)，7.56-7.60(t，1H，J H＝7.8Hz，ArH)，7.68-7.69(d，1H， J H＝7.6Hz，ArH)，7.82-7.84(d，1H，J H＝7.6Hz，ArH)，7.98(s，1H，ArH)
II-10* 2.69(s，3H，CH 3)，5.60(s，2H，CH 2)，7.27-7.33(m，4H，4ArH)，7.41 (s，1H，ArH)，7.58-7.62((t，1H，J H＝7.8Hz，ArH)，7.70-7.72(d，1H， J H＝8.0Hz，ArH)，7.80-7.82(d，1H，J H＝7.6Hz，ArH)，7.93(s，1H，ArH)
II-11 2.69(s，3H，CH 3)，5.60(s，2H，CH 2)，7.30-7.40(m，5H，5ArH)，7.56-7.61 (t，1H，J H＝7.8Hz，ArH)，7.69-7.72(d，1H，J H＝7.8Hz，ArH)，7.78-7.81 (d，1H，J H＝7.8Hz，ArH)，7.93(s，1H，ArH)
II-12 2.70(s，3H，CH 3)，5.69(s，2H，CH 2)，7.06-7.50(m，5H，5ArH)，7.54-7.59 (t，1H，J H＝7.8Hz，ArH)，7.66-7.69(d，1H，J H＝7.8Hz，ArH)，7.79-7.82 (d，1H，J H＝7.8Hz，ArH)，7.95(s，1H，ArH)
II-13 2.70(s，3H，CH 3)，5.63(s，2H，CH 2)，6.96-7.36(m，5H，5ArH)，7.57-7.63 (t，1H，J H＝7.8Hz，ArH)，7.70-7.72(d，1H，J H＝7.8Hz，ArH)，7.81-7.83 (d，1H，J H＝7.5Hz，ArH)，7.94(s，1H，ArH)
II-14 2.71(s，3H，CH 3)，5.82(s，2H，CH 2)，7.33(s，1H，ArH)，7.39-7.44(t， 1H，J H＝7.5Hz，ArH)，7.49-7.70(m，5H，5ArH)，7.79-7.81(d，1H，JH ＝7.5Hz，ArH)，7.95(s，1H，ArH)
II-15 2.35(s，3H，CH 3)，2.69(s，3H，CH 3)，5.60 (s，2H，CH 2)，7.15-7.36(m， 5H，5ArH)，7.54-7.59(t，1H，J H＝8.0Hz，ArH)，7.67-7.69(d，1H，J H＝7.8Hz，ArH)，7.79-7.82(d，1H，J H＝7.8Hz，ArH)，7.94(s，1H，ArH)
II-16 2.71(s，3H，CH 3)，5.87(s，2H，CH 2)，7.21-7.37(m， 4H，4ArH)，7.47-7.53 (t，1H，J H＝7.8Hz，ArH)，7.60-7.62(d，1H，J H＝7.8Hz，ArH)，7.77-7.79 (d，1H，J H＝7.8Hz，ArH)，7.95(s，1H，ArH)
II-17 2.70(s，3H，CH 3)，5.67(s，2H，CH 2)，7.21-7.47(m，4H，4ArH)，7.57-7.62 (t，1H，J H＝7.6Hz，ArH)，7.70-7.72(d，1H，J H＝7.8Hz，ArH)，7.80-7.83 (d，1H，J H＝7.8Hz，ArH)，7.96(s，1 H，ArH)
II-18 2.70(s，3H，CH 3)，5.69(s，2H，CH 2)，7.16-7.32(m，3H，3ArH)，7.49-7.61 (m，3H，3ArH)，7.68-7.71(d，1H，J H＝8.1Hz，ArH)，7.84-7.86(d，1H，
J H＝7.5Hz，ArH)，7.99(s，1H，ArH)
II-19 2.70(s，3H，CH 3)，5.60(s，2H，CH 2)，7.20-7.25(m，1H，ArH)，7.32(s， 1H，ArH)，7.36-7.45(m， 2H，2ArH)，7.57-7.63(m，2H，2ArH)，7.70-7.73 (d，1H，J H＝8.1Hz，ArH)，7.81-7.83(d，1H，J H＝7.8Hz，ArH)，7.92(s， 1H，ArH)
II-20 2.69(s，3H，CH 3)，5.60(s，2H，CH 2)，7.01-7.08(m，2H，2ArH)，7.30 (s，1H，ArH)，7.41-7.45(m，2H，2ArH)，7.55-7.60(t，1H，J H＝7.8Hz， ArH)，7.68-7.71(d，1H，J H＝7.8Hz，ArH)，7.78-7.80(d，1H，J H＝7.5Hz， ArH)，7.93(s，1H，ArH)
II-21 2.38(s，3H，CH 3)，2.92(s，6H，N-CH 3)，5.26(s，2H，CH 2)，6.66-6.69(d， 2H，J H＝8.7Hz，2ArH)，7.17(s，1H，ArH)，7.41-7.44(d，2H，J H＝8.7Hz， 2ArH)，7.50-7.56(t，J H＝8.1Hz，1H，ArH)，7.63-7.66(d，J H＝7.8Hz，1H， ArH)，7.78-7.80(d，J H＝7.5Hz，1H，ArH)，7.93-7.98(m，2H，2ArH)
III-1* 2.59(s，3H，CH 3)，4.51-4.62(b，1H，NH)，4.75-4.60(d，1H，J H＝5.2Hz， CH 2)，6.94(s，1H，pyridazine)，7.26-7.36(m，5H，5ArH)，7.61-7.70 (m，4H，4ArH)
III-2 2.58(s，3H，CH 3)，4.64-4.82(m，3H，NH+CH 2)，6.93-7.72(m，9H，9ArH)
III-3 2.58(s，3H，CH 3)，4.81-4.83(d，1H，J H＝5.7Hz，CH 2)，4.89-4.93(b，1H， NH)，6.93(s，1H，pyridazine)，7.20-7.22(m，2H，2ArH)，7.32-7.37(m， 1H，ArH)，7.56-7.74(m，5H，5ArH)
III-4 2.59(s，3H，CH 3)，4.57-4.61(b，1H，NH)，4.71-4.73(d，1H，J H＝5.7Hz， CH 2)，6.95(s，1H，pyridazine)，7.28-7.32(m，4H，4ArH)，7.62-7.73 (m，4H，4ArH)
III-5 2.61(s，3H，CH 3)，3.80(s，3H，CH 3)，4.42-4.53(b，1H，NH)，4.69-4.71 (d，1H，J H＝5.1Hz，CH 2)，6.85-6.88(m，2H，2ArH)，6.95(s，1H， pyridazine)，7.28-7.32(m，2H，2ArH)，7.63-7.71(m，4H，4ArH)
III-6 2.58(s，3H，CH 3)，2.94-2.98(t，2H，J H＝6.6Hz，CH 2)，3.78-3.84(m，2H， CH 2)，4.08-4.34(b，1H，NH)，6.88(s，1H，pyridazine)，7.12-7.26(m， 5H，5ArH)，7.37-7.40(d，1H，J H＝7.8Hz，ArH)，7.50-7.55(m，2H，2ArH)， 7.66-7.68(d，1H，J H＝7.8Hz，ArH)
III-7 2.59(s，3H，CH 3)，3.55-3.73(b，2H，NH 2)，4.45-4.52(b，1H，NH)， 4.65-4.67(d，1H，J H＝5.4Hz，CH 2)，6.54-6.73(m，3H，3ArH)，6.93(s， 1H，ArH)，7.07-7.12(m，1H，ArH)，7.61-7.71(m，4H，4ArH)
III-8 1.52-1.55(d，1H，J H＝5.4Hz，CH)，2.56(s，3H，CH 3)，4.49-4.56(b，1H， NH)，5.45-5.55(m，1H，CH)，6.90(s，1H，pyridazine)，7.22-7.37(m， 5H，5ArH)，7.63-7.73(m，4H，4ArH)
III-9 2.59(s，3H，CH 3)，3.18-3.22(t，2H，J H＝6.3Hz，CH 2)，3.79-3.85(m，2H， CH 2)，4.35-4.50(b，1H，NH)，6.74-6.75(m，1H，ArH)，6.88-6.91(m， 2H，2ArH)，7.11-7.13(m，1H，ArH)，7.44-7.70(m，4H，4ArH)
III-11 1.48-1.51(d，3H，J H＝6.9Hz，CH 3)，2.55(s，3H，CH 3)，4.42-4.51(b，1H， NH)，5.35-5.47(m，1H，CH)，6.91(s，1H，pyridazine)，7.24-7.31(m， 4H，4ArH)，7.54-7.76(m，4H，4ArH)
III-12 1.49-1.52(d，3H，J H＝6.9Hz，CH3)，2.56(s，3H，CH 3)，4.48-4.51(b，1H， NH)，5.40-5.47(m，1H，CH)，6.91-7.01(m，3H，3ArH)，7.30-7.35(m， 2H，2ArH)，7.58-7.75(m，4H，4ArH)
III-13 2.32(s，3H，CH 3)，2.59(s，3H，CH 3)，4.49-4.52(b，1H，NH)，4.70-4.72 (d，1H，J H＝5.4Hz，CH 2)，6.93(s，1H，pyridazine)，7.11-7.13(d，2H， J H＝7.8Hz，2ArH)，7.23-7.26(d，2H，J H＝8.1Hz，2ArH)，7.60-7.69(m， 4H.4ArH)
* be 400MHz, default to 300MHz
The primary dcreening operation of embodiment 2, application---weeding activity is measured
Pot-culture method (cauline leaf processing): put into a certain amount of soil in the plastics cuvette of diameter 8cm, add a certain amount of water, after planting cover certain thickness soil, cultivate in greenhouse, it is preceding with plastic covered to come up.After emerging, every day in addition quantitative clear water to keep normal growth.Carrying out the cauline leaf spraying when seedling length to the certain period handles.Treatment dosage is the 750g/ hectare.Handle 25 days " Invest, Then Investigate " results, measure the overground part fresh weight, suppress percentage ratio with fresh weight and represent drug effect.
Pot-culture method (soil treatment): put into a certain amount of soil in the plastics cuvette of diameter 8cm, add a certain amount of water, after planting cover certain thickness soil, and in dispenser on the same day, cultivate in greenhouse then, it is preceding with plastic covered to come up.After emerging, every day in addition quantitative clear water to keep normal growth.Carrying out the cauline leaf spraying when seedling length to the certain period handles.Treatment dosage is the 750g/ hectare.Handle 25 days " Invest, Then Investigate " results, measure the overground part fresh weight, suppress percentage ratio with fresh weight and represent drug effect.
Active graded index: ++ +++: 〉=80%; ++ ++: 60～79%; +++: 40～59%; ++: 20～39%; + :≤19%
Table 3: part of compounds (I) weeding activity inhibiting rate (%) (dosage 750g/ hectare) (II)
Compound number The overground part fresh weight suppresses percentage ratio (%)
The barnyard grass grass Lady's-grass Rape Three-coloured amaranth
Cauline leaf is handled Soil treatment Cauline leaf is handled Soil treatment Cauline leaf is handled Soil treatment Cauline leaf is handled Soil treatment
I-2 + ++ + + + + + +
I-3 + ++++ ++ + + + ++ +
I-4 + + + + ++ ++ ++ +++
I-7 + + + + + + + +
I-8 + +++ + + + + + +
I-9 + + + + + + + +
I-11 + +++ + + ++ + + +
I-14 + + ++ + +++ + ++ +
I-15 + ++ + + +++ + ++ +
I-16 ++ ++ + + + + ++ +
I-17 + + + + + + ++ +
II-1 + ++ ++ +++ + + + +
II-2 ++ ++ + + +++++ +++ ++++ ++
II-3 + + + ++ + + ++ +
II-5 ++++ + + + +++++ +++ ++ +++
II-6 + + + + + + ++ +
II-8 + + ++ + ++ + + +
II-9 +++ + ++ ++ +++++ +++ +++ +++
II-10 + ++ + + ++ + ++ +
II-11 + ++ + + ++++ + +++ +
II-12 + + + + ++++ ++ ++ +
II-13 + + + + +++++ + +++ +
II-14 + + + + +++++ ++ +++ +
II-15 + ++ + +++ +++ + ++ +
II-16 + + + +++ ++ + ++ +
II-17 + + + + +++ + ++ +
II-18 + + + ++ +++++ + +++ ++
II-19 + + + + ++++ + ++ +
II-20 + ++ +++ + +++++ + +++ +
II-21 + + + + + + ++ +
III-1 + + ++ + ++ + ++ +
III-2 + + ++ + +++ + +++ ++
III-3 ++ + ++ + ++ ++ ++ +
III-4 + + + + +++ + ++ +
III-5 + ++ + + + + + +
III-6 + + + ++ +++ + ++ +
III 7 + ++ + + + + + +
III-8 + ++ + + + + ++ +
III-9 + + + + ++++ ++ + +
III-11 + ++ + + ++ + ++ +
III-12 + ++ + + ++ + ++ +

Claims (4)

1、一种具有除草活性的三氟甲基苯基哒嗪类衍生物，其特征在于该类衍生物的通式为(I)或(II)：1. A trifluoromethylphenylpyridazine derivative with herbicidal activity, characterized in that the general formula of the derivative is (I) or (II): 其中，in,
Figure A2006101294670002C1
Figure A2006101294670002C1
 R1：H、烷基、烷氧基、苯基、任选取代的苯基、苯基烷氧基、羟基烷基、烷氧烷基、卤代烷基、卤代烷氧基、烷硫基、烯基、卤代烯基、羧基、烷氧基羰基、烷基胺基羰基、二烷基胺基羰基、氨基羰基、卤素、硝基、氰基、烷基胺基、二烷基胺基、乙酰氨基、COR5、NR6R7、3～6元碳环或杂环；R 1 : H, alkyl, alkoxy, phenyl, optionally substituted phenyl, phenylalkoxy, hydroxyalkyl, alkoxyalkyl, haloalkyl, haloalkoxy, alkylthio, alkenyl , haloalkenyl, carboxyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminocarbonyl, halogen, nitro, cyano, alkylamino, dialkylamino, acetamido , COR 5 , NR 6 R 7 , 3-6 membered carbocycle or heterocycle; R2：H、烷基、烷氧基、苯基、任选取代的苯基、苯基烷氧基、羟基烷基、烷氧烷基、卤代烷基、卤代烷氧基、烷硫基、烯基、卤代烯基、羧基、烷氧基羰基、烷基胺基羰基、二烷基胺基羰基、氨基羰基、卤素、硝基、氰基、烷基胺基、二烷基胺基、乙酰氨基、COR5、NR6R7、3～6元碳环或杂环；R 2 : H, alkyl, alkoxy, phenyl, optionally substituted phenyl, phenylalkoxy, hydroxyalkyl, alkoxyalkyl, haloalkyl, haloalkoxy, alkylthio, alkenyl , haloalkenyl, carboxyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminocarbonyl, halogen, nitro, cyano, alkylamino, dialkylamino, acetamido , COR 5 , NR 6 R 7 , 3-6 membered carbocycle or heterocycle; R3：苄基、任选取代的苄基、苯基、任选取代的苯基、H、烷基、羟基烷基、烷氧烷基、卤代烷基、烯基、卤代烯基、酯基、烷氧基羰基、烷基胺基羰基、二烷基胺基羰基、氨基羰基、COR5、SO2R5、3～6元碳环或杂环；R 3 : benzyl, optionally substituted benzyl, phenyl, optionally substituted phenyl, H, alkyl, hydroxyalkyl, alkoxyalkyl, haloalkyl, alkenyl, haloalkenyl, ester , alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminocarbonyl, COR 5 , SO 2 R 5 , 3-6 membered carbocyclic or heterocyclic rings; R4：苄基、任选取代的苄基、苯基、任选取代的苯基、苯基烷基、任选取代的苯基烷基、呋喃基、苯并恶唑基、苯并噻唑基、嘧啶基、吡唑基、哒嗪基、吡啶基、H、烷基、羟基烷基、烷氧烷基、卤代烷基、烯基、卤代烯基、酯基、苄基、COR5、SO2R5、3～6元碳环或杂环，任选取代的呋喃基、苯并恶唑基、苯并噻唑基、嘧啶基、吡唑基、哒嗪、吡啶基；R 4 : benzyl, optionally substituted benzyl, phenyl, optionally substituted phenyl, phenylalkyl, optionally substituted phenylalkyl, furyl, benzoxazolyl, benzothiazolyl , pyrimidinyl, pyrazolyl, pyridazinyl, pyridyl, H, alkyl, hydroxyalkyl, alkoxyalkyl, haloalkyl, alkenyl, haloalkenyl, ester, benzyl, COR 5 , SO 2 R 5 , 3-6 membered carbocycle or heterocycle, optionally substituted furyl, benzoxazolyl, benzothiazolyl, pyrimidinyl, pyrazolyl, pyridazine, pyridyl; X：O、S或N-R8；X: O, S or NR8 ; R5：H、烷基、卤代烷基；R 5 : H, alkyl, haloalkyl; R6、R7：H、烷基；R 6 , R 7 : H, alkyl; R8：H、烷基；R 8 : H, alkyl; 苯环及杂环上的取代基为烷基、烷氧基、卤代烷基、卤代烷氧基，卤素、烷硫基、卤代烷硫基、氰基、硝基，取代基数量为1～5；The substituents on the benzene ring and the heterocycle are alkyl, alkoxy, haloalkyl, haloalkoxy, halogen, alkylthio, haloalkylthio, cyano, nitro, and the number of substituents is 1-5; 所说的烷基是C1～C6的烷基。The said alkyl group is a C 1 -C 6 alkyl group. 2、根据权利要求1所述的具有除草活性的三氟甲基苯基哒嗪类衍生物，其特征在于：2. The herbicidally active trifluoromethylphenylpyridazine derivatives according to claim 1, characterized in that: 所说的R1是甲基、三氟甲基、氯、溴、甲氧基、乙氧基、甲氨基、二甲氨基、苯基、间三氟甲基苯基、间甲氧基苯基、间溴苯基、间甲基苯基、邻三氟甲基苯基、邻甲氧基苯基、邻溴苯基、邻甲基苯基、对三氟甲基苯基、对甲氧基苯基、对溴苯基、对甲基苯基；Said R is methyl, trifluoromethyl, chlorine, bromine, methoxy, ethoxy, methylamino, dimethylamino, phenyl, m-trifluoromethylphenyl, m-methoxyphenyl , m-bromophenyl, m-methylphenyl, o-trifluoromethylphenyl, o-methoxyphenyl, o-bromophenyl, o-methylphenyl, p-trifluoromethylphenyl, p-methoxy Phenyl, p-bromophenyl, p-methylphenyl; R2是氢、甲基、三氟甲基、氯、溴、甲氧基、乙氧基、甲氨基、二甲氨基、苯基、间三氟甲基苯基、间甲氧基苯基、间溴苯基、间甲基苯基、邻三氟甲基苯基、邻甲氧基苯基、邻溴苯基、邻甲基苯基、对三氟甲基苯基、对甲氧基苯基、对溴苯基、对甲基苯基； R is hydrogen, methyl, trifluoromethyl, chloro, bromo, methoxy, ethoxy, methylamino, dimethylamino, phenyl, m-trifluoromethylphenyl, m-methoxyphenyl, m-bromophenyl, m-methylphenyl, o-trifluoromethylphenyl, o-methoxyphenyl, o-bromophenyl, o-methylphenyl, p-trifluoromethylphenyl, p-methoxybenzene Base, p-bromophenyl, p-methylphenyl; R3是对硝基苄基、间硝基苄基、邻硝基苄基、邻氟苄基、间氟苄基、对氟苄基、2，4-二氟苄基、2，6-二氟苄基、2-氰基苄基、3-氰基苄基、4-氰基苄基、2-氯苄基、3-氯苄基、4-氯苄基、2-溴苄基、3-溴苄基、4-溴苄基、2-甲氧基苄基、3-甲氧基苄基、4-甲氧基苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、苄基、4-特丁基苄基、2-氯-5-吡啶苄基、2-甲氧羰基-5-吡啶苄基；R 3 is p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, o-fluorobenzyl, m-fluorobenzyl, p-fluorobenzyl, 2,4-difluorobenzyl, 2,6-di Fluorobenzyl, 2-cyanobenzyl, 3-cyanobenzyl, 4-cyanobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3 -Bromobenzyl, 4-bromobenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-methylbenzyl, 3-methylbenzyl, 4 -Methylbenzyl, benzyl, 4-tert-butylbenzyl, 2-chloro-5-pyridylbenzyl, 2-methoxycarbonyl-5-pyridylbenzyl; R4是邻氟苄基、间氟苄基、对氟苄基、2，4-二氟苄基、2，6-二氟苄基、2-氰基苄基、3-氰基苄基、4-氰基苄基、2-氯苄基、3-氯苄基、4-氯苄基、2-溴苄基、3-溴苄基、4-溴苄基、2-甲氧基苄基、3-甲氧基苄基、4-甲氧基苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、3，5-二甲基苄基、2-三氟甲基苄基、3-三氟甲基苄基、4-三氟甲基苄基、2，6-二氯苄基、2，4-二氯苄基、4-二甲氨基苄基、3-氨基苄基、苯乙基、α甲基苄基[C6H5CH(CH3)]、2-噻酚乙基[2-thiophene-CH2CH2]、2-呋喃苄基[2-furan-CH2]、α甲基4-氯苄基[4-ClC6H4CH(CH3)]、α甲基4-氟苄基[4-FC6H4CH(CH3)]。R is o -fluorobenzyl, m-fluorobenzyl, p-fluorobenzyl, 2,4-difluorobenzyl, 2,6-difluorobenzyl, 2-cyanobenzyl, 3-cyanobenzyl, 4-cyanobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-methoxybenzyl , 3-methoxybenzyl, 4-methoxybenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 3,5-dimethylbenzyl, 2- Trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,6-dichlorobenzyl, 2,4-dichlorobenzyl, 4-dimethylaminobenzyl , 3-aminobenzyl, phenethyl, α-methylbenzyl[C 6 H 5 CH(CH 3 )], 2-thiopheneethyl[2-thiophene-CH 2 CH 2 ], 2-furylbenzyl [2-furan-CH 2 ], α-methyl 4-chlorobenzyl [4-ClC 6 H 4 CH(CH 3 )], α-methyl 4-fluorobenzyl [4-FC 6 H 4 CH(CH 3 )]. 3、一种权利要求1所述的衍生物的制备方法，其特征在于它是经过下述步骤完成：3. A method for preparing the derivative according to claim 1, characterized in that it is completed through the following steps: (1)原甲酸三甲酯与溴丙酮混合，其中摩尔比为1∶0.5～1，加入醇类溶剂及浓硫酸，混合物在0～90℃反应0.5～48小时后中和，减压蒸馏得到产物1-溴-2，2-二甲氧基丙烷；(1) Trimethyl orthoformate is mixed with bromoacetone, wherein the molar ratio is 1:0.5~1, alcohol solvent and concentrated sulfuric acid are added, the mixture is reacted at 0~90°C for 0.5~48 hours, then neutralized, and distilled under reduced pressure to obtain Product 1-bromo-2,2-dimethoxypropane; (2)将上步中得到的1-溴-2，2-二甲氧基丙烷与催化量的二异丙基乙基胺对甲苯磺酸盐混合加热到40～240℃，蒸馏得到3-溴-2-甲氧基丙烯和2-甲氧基烯丙基溴的混合物；(2) Mix the 1-bromo-2,2-dimethoxypropane obtained in the previous step with a catalytic amount of diisopropylethylamine p-toluenesulfonate and heat it to 40-240°C, and distill it to obtain 3- Mixtures of bromo-2-methoxypropene and 2-methoxyallyl bromide; (3)氢化钠与溶剂N，N-二甲基甲酰胺混合后加入间三氟甲基苯乙酸乙酯的DMF溶液，搅拌0.5～4小时后加入上步中得到的3-溴-2-甲氧基丙烯和2-甲氧基烯丙基溴的DMF溶液，摩尔比为1～2∶1∶1～4，0～120℃反应1～48小时，反应液冷却后酸化，萃取、干燥，有机相旋干后得到4-氧代-2-(3-三氟甲基苯基)-戊酸乙酯的粗品；将4-氧代-2-(3-三氟甲基苯基)-戊酸乙酯的粗品与水合肼混合，摩尔比为1∶1～2，加入醇类溶剂，加热回流0.5～24小时，将混合物倒入水中，抽滤得到6-甲基-4-(3-三氟甲基苯基)-4，5-二氢-3(2H)哒嗪酮黄色固体；(3) Sodium hydride is mixed with the solvent N, N-dimethylformamide, then added to the DMF solution of ethyl m-trifluoromethylphenylacetate, stirred for 0.5 to 4 hours, and then added the 3-bromo-2- DMF solution of methoxypropene and 2-methoxyallyl bromide, the molar ratio is 1~2:1:1~4, react at 0~120°C for 1~48 hours, acidify the reaction solution after cooling, extract and dry , the organic phase was spin-dried to obtain the crude product of 4-oxo-2-(3-trifluoromethylphenyl)-pentanoic acid ethyl ester; 4-oxo-2-(3-trifluoromethylphenyl) -The crude product of ethyl valerate is mixed with hydrazine hydrate, the molar ratio is 1:1~2, alcohol solvent is added, heated to reflux for 0.5~24 hours, the mixture is poured into water, and 6-methyl-4-( 3-trifluoromethylphenyl)-4,5-dihydro-3(2H)pyridazinone yellow solid; (4)将上步中得到的6-甲基-4-(3-三氟甲基苯基)-4，5-二氢-3(2H)哒嗪酮与无水碳酸钾粉末在二甲基亚砜中混合，摩尔比为1∶1～2，0～90℃时搅拌0.5～24小时，将反应液倒入水中，萃取，干燥，旋干后得到黄色固体，为6-甲基-4-(3-三氟甲基苯基)-3(2H)哒嗪酮；(4) 6-methyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-3(2H)pyridazinone obtained in the previous step and anhydrous potassium carbonate powder were dissolved in dimethyl Mixed with sulfoxide, the molar ratio is 1:1~2, stirred at 0~90°C for 0.5~24 hours, poured the reaction solution into water, extracted, dried, and spin-dried to obtain a yellow solid, which was 6-methyl- 4-(3-trifluoromethylphenyl)-3(2H)pyridazinone; (5)将氢化钠与无水N，N-二甲基甲酰胺混合，加入上步中得到的6-甲基-4-(3-三氟甲基苯基)-3(2H)哒嗪酮，摩尔比为1～2∶1，搅拌至全部溶解，加入1～2倍量的卤代物，0～110℃下反应1～48小时，反应液旋干，残余物用柱层析分离，得到固体或液体为N-取代-6-甲基-4-(3-三氟甲基苯基)-3(2H)-哒嗪酮；(5) Mix sodium hydride with anhydrous N,N-dimethylformamide, add 6-methyl-4-(3-trifluoromethylphenyl)-3(2H)pyridazine obtained in the previous step Ketone, the molar ratio is 1-2:1, stir until it is completely dissolved, add 1-2 times the amount of halide, react at 0-110°C for 1-48 hours, spin the reaction solution to dryness, and separate the residue by column chromatography. The obtained solid or liquid is N-substituted-6-methyl-4-(3-trifluoromethylphenyl)-3(2H)-pyridazinone; (6)将上步中得到的6-甲基-4-(3-三氟甲基苯基)-3(2H)哒嗪酮与三氯氧磷混合，0～100℃时搅拌0.5～24小时，三氯氧磷蒸除后残余物倒入水中，抽滤得到白色固体，为3-氯-6-甲基-4-(3-三氟甲基苯基)-哒嗪；(6) Mix 6-methyl-4-(3-trifluoromethylphenyl)-3(2H)pyridazinone obtained in the previous step with phosphorus oxychloride, and stir at 0-100°C for 0.5-24 Hours, the phosphorus oxychloride was evaporated and the residue was poured into water, and suction filtered to obtain a white solid, which was 3-chloro-6-methyl-4-(3-trifluoromethylphenyl)-pyridazine; (7)将氢化钠与无水N，N-二甲基甲酰胺混合，加入(取代)苄醇，摩尔比为1～2∶1，搅拌至全部溶解，加入1～2倍量的上步中得到的3-氯-6-甲基-4-(3-三氟甲基苯基)-哒嗪，0～110℃下反应1～48小时，反应液倒入水中，收集得到的固体，为3-(取代)苄氧基-6-甲基-4-(3-三氟甲基苯基)-哒嗪；(7) Mix sodium hydride with anhydrous N, N-dimethylformamide, add (substituted) benzyl alcohol, the molar ratio is 1-2:1, stir until all dissolve, add 1-2 times the amount of the previous step The 3-chloro-6-methyl-4-(3-trifluoromethylphenyl)-pyridazine obtained in , was reacted at 0-110°C for 1-48 hours, the reaction solution was poured into water, and the obtained solid was collected. is 3-(substituted)benzyloxy-6-methyl-4-(3-trifluoromethylphenyl)-pyridazine; (8)将上步得到的3-氯-6-甲基-4-(3-三氟甲基苯基)-哒嗪与(取代)苄胺混合，在100～250℃反应1～72小时，柱层析分离得到产物3-(取代)苄胺基-6-甲基-4-(3-三氟甲基苯基)-哒嗪。(8) Mix the 3-chloro-6-methyl-4-(3-trifluoromethylphenyl)-pyridazine obtained in the previous step with (substituted) benzylamine and react at 100-250°C for 1-72 hours , separated by column chromatography to obtain the product 3-(substituted)benzylamino-6-methyl-4-(3-trifluoromethylphenyl)-pyridazine. 4、一种权利要求1所述的衍生物的应用，其特征在于，作为白化除草剂，用于防除禾本科杂草及阔叶杂草。4. The application of the derivative according to claim 1, characterized in that it is used as an albino herbicide for controlling gramineous weeds and broad-leaved weeds.
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USRE47142E1 (en) 2008-06-03 2018-11-27 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US8304413B2 (en) 2008-06-03 2012-11-06 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
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