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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benzyl
trifluoromethyl
methyl
phenyl
group
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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

The invention discloses a trifluoromethyl phenyl pyridazine derivant and preparing method with weeding activity for compounds (I) and (II), wherein R1 is H, alkyl, phenyl, substituted benzene, alkoxy, phenyl alkoxy, hydroxyalkyl, alkoxy alkyl, halogenated alkyl group, halogenated alkoxy, nitro, cyano, alkylamine, dialkylamine and acetylamino; R2 is H, alkyl, phenyl, substituted benzene, alkoxy, phenyl alkoxy, hydroxyalkyl, alkoxy alkyl, halogenated alkyl group, halogenated alkoxy, nitro, cyano, alkylamine, dialkylamine and acetylamino; R3 is H, benzyl, substituted benzyl, alkyl, hydroxy alkyl, alkoxy alkyl, halogenated alkyl groups, olefin base and halogenated olefin; R4 is benzyl, substituted benzyl, phenyl, substituted phenyl; X is O, NH and S.

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, a kind of trifluoromethyl pyridazine class derivative with weeding activity, the general formula that it is characterized in that this analog derivative be for (I) or (II):
Wherein,
Figure A2006101294670002C1
R 1: H, alkyl, alkoxyl group, phenyl, optional phenyl, phenyl alkoxyl group, hydroxyalkyl, alkoxyalkyl, haloalkyl, 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 2: H, alkyl, alkoxyl group, phenyl, optional phenyl, phenyl alkoxyl group, hydroxyalkyl, alkoxyalkyl, haloalkyl, 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 6, R 7: H, alkyl;
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.
2, the trifluoromethyl pyridazine class derivative with weeding activity according to claim 1 is characterized in that:
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)].
3, the preparation method of the described derivative of a kind of claim 1 is characterized in that it is to finish through following step:
(1) trimethyl orthoformate mixes with martonite, and wherein mol ratio is 1: 0.5～1, adds the alcoholic solvent and 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 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone yellow solid;
(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.
4, the application of the described derivative of a kind of claim 1 is characterized in that, as bleaching herbicide, is used to prevent and kill off gramineous weeds and broadleaf weeds.
CN 200610129467 2006-11-21 2006-11-21 Trifluoromethylphenylpyridazine derivative and its preparation method Pending CN1962642A (en)

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US8304413B2 (en) 2008-06-03 2012-11-06 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US8884010B2 (en) 2010-09-08 2014-11-11 Sumitomo Chemical Company, Limited Method for producing pyridazinone compounds and intermediate thereof
US9359379B2 (en) 2012-10-02 2016-06-07 Intermune, Inc. Anti-fibrotic pyridinones
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Publication number Priority date Publication date Assignee Title
CN101058562B (en) * 2007-06-06 2010-05-19 南开大学 3-substituted oxypyridazine derivative with weeding activity and preparation method thereof
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
US8969347B2 (en) 2008-06-03 2015-03-03 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US9290450B2 (en) 2008-06-03 2016-03-22 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US8884010B2 (en) 2010-09-08 2014-11-11 Sumitomo Chemical Company, Limited Method for producing pyridazinone compounds and intermediate thereof
US9040709B2 (en) 2010-09-08 2015-05-26 Sumitomo Chemical Company, Limited Method for producing pyridazinone compounds and intermediate thereof
US9359379B2 (en) 2012-10-02 2016-06-07 Intermune, Inc. Anti-fibrotic pyridinones
US9675593B2 (en) 2012-10-02 2017-06-13 Intermune, Inc. Anti-fibrotic pyridinones
US10376497B2 (en) 2012-10-02 2019-08-13 Intermune, Inc. Anti-fibrotic pyridinones
US10898474B2 (en) 2012-10-02 2021-01-26 Intermune, Inc. Anti-fibrotic pyridinones
US10233195B2 (en) 2014-04-02 2019-03-19 Intermune, Inc. Anti-fibrotic pyridinones
US10544161B2 (en) 2014-04-02 2020-01-28 Intermune, Inc. Anti-fibrotic pyridinones

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