CN101058563A - 3-substituted amidopyridazine derivative with weeding activity and preparation method thereof - Google Patents
3-substituted amidopyridazine derivative with weeding activity and preparation method thereof Download PDFInfo
- Publication number
- CN101058563A CN101058563A CN 200710057564 CN200710057564A CN101058563A CN 101058563 A CN101058563 A CN 101058563A CN 200710057564 CN200710057564 CN 200710057564 CN 200710057564 A CN200710057564 A CN 200710057564A CN 101058563 A CN101058563 A CN 101058563A
- Authority
- CN
- China
- Prior art keywords
- trifluoromethyl
- phenyl
- solvent
- methyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a 3-substituted aminopyridazine compound and making method, which possesses weeding activity with structure as formula (I), wherein R1 and 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 phenyl, substituted phenyl and so on; R4 is H, alkyl and so on. The invention improves weeding activity and whitening activity more than the compound in the CN 200610129467. 1, which displays more projecting at selectivity of crop.
Description
[technical field]: the present invention relates to the technical field of weedicide and preparation thereof, the preparation of particularly a kind of 3-substituted-amino pyridazine compound, compound and as herbicide applications.
[background technology]: in high green plants, carotenoid has important effect.It is the integral part of synthetic photosynthetic cells device, is used for forming photosynthetic reaction center; In photoabsorption, carotenoid has been born the effect of electron transport among the photosynthetical system II as accessory pigment; Carotenoid still is the protective substance in the photosynthesis, and it can protect photosynthetical system, particularly under high light pressure, and the triplet state chlorophyll oxidation that avoids being excited.In the presence of bleaching herbicide, carotenoid is synthetic to be suppressed, and the reduction of concentration makes it can not bring into play effective provide protection, and is final under the irradiation of intense light, chlorophyll degradation, and plant shows typical albinism.Therefore, the mode of action of bleaching herbicide is by suppressing the synthetic of carotenoid, causing the active reduction of plant photosynthesis.Most of coml bleaching herbicides all are the phytoene dehydrogenases that suppress to contain in the oxygen photosynthesis.
[summary of the invention]: the purpose of this invention is to provide 3-substituted-amino pyridazine compound and their preparation method and application.Compound of the present invention has higher weeding activity to annual gramineous weed and broadleaf weeds, and crop is shown good selectivity.
The general formula of The compounds of this invention is (I):
Wherein,
R
1, 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: 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;
R
4: H, alkyl;
R
5: H, alkyl, haloalkyl;
R
6, R
7: 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
1, R
2Be hydrogen, methyl, trifluoromethyl, chlorine, bromine, methoxyl group, oxyethyl group, methylamino-, dimethylamino, phenyl;
R
3It is phenyl, the 2-fluorophenyl, the 3-fluorophenyl, the 4-fluorophenyl, 2, the 3-difluorophenyl, 2, the 4-difluorophenyl, 2, the 5-difluorophenyl, 2, the 6-difluorophenyl, 3, the 4-difluorophenyl, 3, the 5-difluorophenyl, the 2-cyano-phenyl, the 3-cyano-phenyl, the 4-cyano-phenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, 2, the 3-dichlorophenyl, 2, the 4-dichlorophenyl, 2, the 5-dichlorophenyl, 2, the 6-dichlorophenyl, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, the 2-bromophenyl, the 3-bromophenyl, the 4-bromophenyl, 2, the 3-dibromo phenyl, 2, the 4-dibromo phenyl, 2, the 5-dibromo phenyl, 2, the 6-dibromo phenyl, 3, the 4-dibromo phenyl, 3, the 5-dibromo phenyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, 2, the 4-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 3, the 5-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, the 2-trifluoromethyl, the 3-trifluoromethyl, the 4-trifluoromethyl, the 4-Trifluoromethoxyphen-l, the 4-tert-butyl-phenyl, the 2-phenyl;
R
4Be hydrogen, methyl.
The synthetic route of The compounds of this invention (I) is as follows:
Concrete preparation method, finish through following steps:
(1) be 1: 1～2 to mix in molar ratio with 3-trifluoromethyl phenylacetic acid and dehydrated alcohol, under making solvent, benzene reacts, add 100～300ml benzene solvent in every mole of 3-trifluoromethyl phenylacetic acid reactant, and the vitriol oil that adds 0.5～2 times of amount dewaters, heat 40～120 ℃, 6～48 hours, anhydrate with the water trap branch; After reaction finishes reaction solution is poured in the water, be neutralized to neutrality, isolate oil reservoir, the water layer extracted with diethyl ether merges organic layer, and drying is filtered, boil off solvent after, underpressure distillation, 116～120 ℃/18mmHg of collection cut obtains 3-trifluoromethyl phenylacetic acid ethyl ester;
(2) in carbon tetrachloride solvent, the 3-trifluoromethyl phenylacetic acid ethyl ester that the step makes in the adding, and N-bromosuccinimide (NBS), mol ratio is 1: 1～2, and drip 48% hydrobromic acid solution initiation reaction, reacted 2～48 hours down at 0～150 ℃, wherein, add 500～2000ml carbon tetrachloride solvent in every mole of 3-trifluoromethyl phenylacetic acid ethyl ester and add the 1ml hydrobromic acid solution; Reaction after finishing is removed the solid filtering in the reaction solution, after solvent is sloughed in decompression, obtains colourless transparent liquid, is bromo-3-trifluoromethyl ethyl acetate;
(3) in acetone solvent, the step makes in the adding bromo-3-trifluoromethyl ethyl acetate, methyl aceto acetate and Anhydrous potassium carbonate powder, mol ratio is 1: 1～2: 1～3, react 0.5～8 hour down to reacting completely at 0～100 ℃, wherein, add 1000～3000ml acetone solvent in every mole bromine generation-3-trifluoromethyl ethyl acetate; After reaction solution is sloughed solvent, use dichloromethane extraction, extraction liquid saturated common salt water washing, drying after solvent is sloughed in decompression, obtains the crude product of 2-ethanoyl-3-(3-trifluoromethyl)-diethyl succinate, can be directly used in next step reaction;
(4) go up and to add 40% NaOH solution in the crude product of 2-ethanoyl-3-(3-trifluoromethyl)-diethyl succinate that the step makes, mol ratio is 1: 3～7, stirs down 0～100 ℃ of reaction 1～8 hour down, and reaction adds hcl acidifying; Reaction solution after the acidifying was 0～100 ℃ of reaction 1～10 hour, and the reaction solution organic solvent extraction filters, and is spin-dried for, and obtains the crude product of 4-oxo-2-(3-trifluoromethyl)-valeric acid, can be directly used in next step reaction;
(5) in alcohol solvent, the crude product and 85% hydrazine hydrate solution of 4-oxo-2-(3-trifluoromethyl)-valeric acid that the step makes in the adding, mol ratio is 1: 1～3,0～80 ℃ was reacted 1～10 hour, wherein, every mole of 4-oxo-2-(3-trifluoromethyl)-valeric acid adds 500～3000ml alcohol solvent; Reaction solution is poured in the water, had light yellow solid to separate out, filter out solid, drying obtains 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone;
(6) in dimethyl sulfoxide solvent, 6-methyl-4-(3-trifluoromethyl)-4 that the step makes in the adding, 5-dihydro-3 (2H) pyridazinone and Anhydrous potassium carbonate powder, mol ratio is 1: 1～5,0～80 ℃ was reacted 1～48 hour down, wherein, every mole of 6-methyl-4-(3-trifluoromethyl)-4 adds 3000～4000ml dimethyl sulfoxide solvent in 5-dihydro-3 (2H) pyridazinone; Reactant is poured in the water, with dilute hydrochloric acid neutralization, solvent extraction, washing, drying, slough solvent after, obtain 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone;
(7) in the phosphorus oxychloride solvent, 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone that the step makes in the adding, stirred 0.5～24 hour in the time of 0～100 ℃, boil off unnecessary phosphorus oxychloride, resistates is poured in the water, and suction filtration gets white solid, is 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine, wherein, add 5000～6000ml phosphorus oxychloride solvent in every mole of 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone;
(8) go up 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine and the substituted aniline Hybrid Heating that the step makes, mol ratio is 1: 1～10; Mixture is 50～220 ℃ of reactions 1～24 hour, after the cooling, with organic solvent with the reaction solution stripping, washing, drying is filtered, and directly uses column chromatography after concentrated and obtains 3-substituted-amino-6-methyl-4-(3-trifluoromethyl) pyridazine.
Described application of compound as bleaching herbicide, can be prevented and kill off annual broadleaf weed and gramineous weeds.
Advantage of the present invention and effect: the active aspect of the weeding activity of the 3-substituted-amino pyridazine compound that relates among the present invention and albefaction is enhanced than the compound of report among the patent CN 200610129467.1, 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 gramineous crop is shown good selectivity, can the direct dispenser in farmland under 75～150 gram/hectare dosage.
[embodiment]:
Synthesizing of embodiment 1:3-trifluoromethyl phenylacetic acid ethyl ester
In flask at the bottom of the 250ml garden, add 53.86g (0.26mmol) 3-trifluoromethyl phenylacetic acid, the 80ml dehydrated alcohol, 60ml benzene, the 12ml vitriol oil anhydrates with the water trap branch, 80 ℃ of reaction 36h, tell 10ml water in the water trap approximately, stop heating, reaction solution is poured in the 240ml frozen water, add potassium carbonate powder under stirring to neutral, oil reservoir is separated, (3 * 75mL) extractions merge organic layer to water layer, use anhydrous magnesium sulfate drying with ether, filter, after sloughing solvent, use underpressure distillation, collect 116～120 ℃/18mmHg cut (100 ℃ of literature values/10mmHg), get colourless liquid 3-trifluoromethyl phenylacetic acid ethyl ester, yield 92.84%.
Embodiment 2: bromo 3-trifluoromethyl ethyl acetate synthetic
23.2g (100mmol) 3-trifluoromethyl phenylacetic acid ethyl ester, 100ml carbon tetrachloride solution and 18.7g (105mmol) N-bromosuccinimide (NBS), drip 2 hydrobromic acid solutions (48%) initiation reaction, this moment, reaction solution was orange red, and room temperature reaction 48 hours after the reaction is removed the solid filtering in the reaction solution, after filtrate is sloughed solvent, get colourless transparent liquid bromo-3-trifluoromethyl ethyl acetate, yield 96.4%
1H NMR (300MHz) δ: 1.27-1.32 (t, J
H=7.2Hz, 3H, CH
3), 4.24-4.28 (m, 2H, CH
2), 5.35 (s, 1H, CH), 7.48-7.53 (t, J
H=7.6Hz, 1H, ArH), 7.60-7.63 (d, J
H=7.8Hz, 1H, ArH), 7.75-7.78 (d, J
H=7.8Hz, 1H, ArH), 7.81 (s, 1H, ArH).
Embodiment 3: bromo-3-trifluoromethyl ethyl acetate synthetic
23.2g (100mmol) 3-trifluoromethyl phenylacetic acid ethyl ester, 100ml carbon tetrachloride solution and 18.7g (105mmol) N-bromosuccinimide (NBS), drip 2 hydrobromic acid solutions (48%) initiation reaction, this moment, reaction solution was orange red, 50 ℃ were reacted 36 hours, and after the reaction solid filtering in the reaction solution were removed, after filtrate is sloughed solvent, get colourless transparent liquid bromo-3-trifluoromethyl ethyl acetate, yield 94.1%.
Embodiment 4: bromo-3-trifluoromethyl ethyl acetate synthetic
In the 250ml round-bottomed bottle, add 23.2g (100mmol) 3-trifluoromethyl phenylacetic acid ethyl ester, 100ml carbon tetrachloride solution and 18.7g (105mmol) N-bromosuccinimide (NBS) drips 2 hydrobromic acid solutions (48%) initiation reaction, this moment, reaction solution was orange red, reflux 16h.Stop heating, the solid filtering in the reaction solution is removed, after filtrate is sloughed solvent, get colourless transparent liquid bromo-3-trifluoromethyl ethyl acetate, yield 98.4%.
Synthesizing of embodiment 5:2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate
15.6g (50mmol) bromo-3-trifluoromethyl ethyl acetate, 6.5g (50mmol) methyl aceto acetate, 100ml acetone and 7.6g (55mmol) Anhydrous potassium carbonate powder, room temperature reaction 8 hours.After reaction finishes; slough solvent; add 100ml water; with methylene dichloride (3 * 75ml) extraction, saturated nacl aqueous solution (2 * 50ml) washing organic phases after, drying; slough solvent; obtain the tawny thick liquid, the crude product for 2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate can be directly used in next step reaction.
Synthesizing of embodiment 6:2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate
15.6g (50mmol) bromo-3-trifluoromethyl ethyl acetate, 6.5g (50mmol) methyl aceto acetate, 100ml acetone and 7.6g (55mmol) Anhydrous potassium carbonate powder, 40 ℃ were reacted 6 hours.After reaction finishes; slough solvent; add 100ml water; with methylene dichloride (3 * 75ml) extraction, saturated nacl aqueous solution (2 * 50ml) washing organic phases after, drying; slough solvent; obtain the tawny thick liquid, the crude product for 2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate can be directly used in next step reaction.
Synthesizing of embodiment 7:2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate
In the 250ml round-bottomed bottle, add 15.6g (50mmol) bromo-3-trifluoromethyl ethyl acetate, 6.5g (50mmol) methyl aceto acetate, 100ml acetone and 7.6g (55mmol) Anhydrous potassium carbonate powder, reflux 2h is to reacting completely under stirring.After reaction finishes; slough solvent; add 100ml water; with methylene dichloride (3 * 75ml) extraction, saturated nacl aqueous solution (2 * 50ml) washing organic phases after, drying; slough solvent; obtain the tawny thick liquid, the crude product for 2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate can be directly used in next step reaction.
Synthesizing of embodiment 8:4-oxo-2-(3-trifluoromethyl) valeric acid
In the crude product of 2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate that last step makes, adding 100ml concentration is the NaOH solution of 2.5mmol/L, and stirring at room 4h slowly adds the concentrated hydrochloric acid acidifying after reaction finishes, and 100 ℃ are stirred 1h down.After reaction finishes, with methylene dichloride (3 * 75ml) extractive reaction liquid, organic phase anhydrous magnesium sulfate drying filter, slough solvent after, must the tawny thick liquid, the crude product for 4-oxo-2-(3-trifluoromethyl) valeric acid can be directly used in next step reaction.
Synthesizing of embodiment 9:4-oxo-2-(3-trifluoromethyl) valeric acid
In the crude product of 2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate that last step makes, adding 100ml concentration is the NaOH solution of 2.5mmol/L, and 50 ℃ are stirred 4h, slowly adds the concentrated hydrochloric acid acidifying after reaction finishes, and 50 ℃ are stirred 1h down.After reaction finishes, with methylene dichloride (3 * 75ml) extractive reaction liquid, organic phase anhydrous magnesium sulfate drying filter, slough solvent after, must the tawny thick liquid, the crude product for 4-oxo-2-(3-trifluoromethyl) valeric acid can be directly used in next step reaction.
Synthesizing of embodiment 10:4-oxo-2-(3-trifluoromethyl) valeric acid
In the crude product of 2-ethanoyl-3-(3-trifluoromethyl) diethyl succinate that last step makes, adding 100ml concentration is the NaOH solution of 2.5mmol/L, and 100 ℃ are stirred 2h, slowly adds concentrated hydrochloric acid acidifying, stirring at room 1h after reaction finishes.After reaction finishes, with methylene dichloride (3 * 75ml) extractive reaction liquid, organic phase anhydrous magnesium sulfate drying filter, slough solvent after, must the tawny thick liquid, the crude product for 4-oxo-2-(3-trifluoromethyl) valeric acid can be directly used in next step reaction.
Embodiment 11:6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone synthetic
In the crude product of 4-oxo-2-(3-trifluoromethyl) valeric acid, add ethanol 70ml, mixing and stirring slowly drips 85% hydrazine hydrate solution 2.9g, the reaction solution heat release, after dropwising, stirring at room 6h.After the reaction solution cooling, slowly be added drop-wise in the 250ml frozen water, and constantly stir, there is light yellow solid to separate out, filter out yellow solid, drying gets 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone.
Embodiment 12:6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone synthetic
In the crude product of 4-oxo-2-(3-trifluoromethyl) valeric acid, add ethanol 70ml, mixing and stirring slowly drips 85% hydrazine hydrate solution 2.9g, the reaction solution heat release, after dropwising, 50 ℃ of reaction 4h down.After the reaction solution cooling, slowly be added drop-wise in the 250ml frozen water, and constantly stir, there is light yellow solid to separate out, filter out yellow solid, drying gets 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone.
Embodiment 13:6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone synthetic
In the crude product of 4-oxo-2-(3-trifluoromethyl) valeric acid, add ethanol 70ml, mixing and stirring slowly drips 85% hydrazine hydrate solution 2.9g, the reaction solution heat release, after dropwising, back flow reaction 3h.After the reaction solution cooling, slowly be added drop-wise in the 250ml frozen water, and constantly stir, there is light yellow solid to separate out, filter out yellow solid, drying gets 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone.mp 127-129℃；
1H NMR(400MHz)δ：2.09(s，3H，CH
3)，2.72-2.87(m，2H，CH
2)，3.73-3.77(m，1H，CH)，7.42-7.44(d，J
H＝7.6Hz，1H，ArH)，7.48-7.51(m，2H，2ArH)，7.56-7.58(d，J
H＝8.0Hz，1H，ArH)，8.48(s，1H，NH)；MS，m/z：256(M
+)；Anal：calc for C
12H
11F
3N
2O；C 56.25，H 4.33，N 10.93；found C 56.20，H 4.38，N11.02.。With bromo-3-trifluoromethyl ethyl acetate is that raw material calculating total recovery is 55.7%.
Synthesizing of embodiment 14:6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone
With 7.13g (27.9mmol) 4,5-dihydro-4-(3-trifluoromethyl)-6-methyl-3 (2H) pyridazinone, the mixture of 3.85g (27.9mmol) Anhydrous potassium carbonate powder and 100ml dimethyl sulfoxide (DMSO) stirs 48h.Reactant is poured in the 200ml water, neutralize with 15% dilute hydrochloric acid, 100ml saturated common salt water washing 2 times of 100ml ether extraction 5 times, organic phase, concentrating under reduced pressure obtains 6.73g white solid 4-(3-trifluoromethyl)-6-methyl-3 (2H) pyridazinone behind the anhydrous magnesium sulfate drying.
Synthesizing of embodiment 15:6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone
With 7.13g (27.9mmol) 4,5-dihydro-4-(3-trifluoromethyl)-6-methyl-3 (2H) pyridazinone, the mixture of 3.85g (27.9mmol) Anhydrous potassium carbonate powder and 100ml dimethyl sulfoxide (DMSO) stirs 36h down at 50 ℃.Reactant is poured in the 200ml water, neutralize with 15% dilute hydrochloric acid, 100ml saturated common salt water washing 2 times of 100ml ether extraction 5 times, organic phase, concentrating under reduced pressure obtains 6.73g white solid 4-(3-trifluoromethyl)-6-methyl-3 (2H) pyridazinone behind the anhydrous magnesium sulfate drying.
Synthesizing of embodiment 16:6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone
With 7.13g (27.9mmol) 4,5-dihydro-4-(3-trifluoromethyl)-6-methyl-3 (2H) pyridazinone, the mixture of 3.85g (27.9mmol) Anhydrous potassium carbonate powder and 100ml dimethyl sulfoxide (DMSO) stirs 24h down at 80 ℃.Reactant is poured in the 200ml water, neutralize with 15% dilute hydrochloric acid, 100ml saturated common salt water washing 2 times of 100ml ether extraction 5 times, organic phase, concentrating under reduced pressure obtains 6.73g white solid 4-(3-trifluoromethyl)-6-methyl-3 (2H) pyridazinone behind the anhydrous magnesium sulfate drying.Mp 175-176 ℃;
1H NMR (400MHz) δ: 2.42 (s, 3H, CH
3), 7.32 (s, 1H, pyridazinone), 7.57-7.60 (t, J
H=7.8Hz, 1H, ArH), 7.68-7.70 (d, J
H=7.6Hz, 1H, ArH), 8.02 (s, 1H, ArH), 8.09-8.11 (d, J
H=7.6Hz, 1H, ArH), 11.77 (s, 1H, NH); MS, m/z:254 (M
+); Anal:calcd for C
12H
9F
3N
2O; C 56.70, and H 3.57, and N 11.02; Found C 56.72, H 3.60, and N 11.06, yield 95.0%.
Synthesizing of embodiment 17:3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine
In a round-bottomed bottle, add 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone 2g (7.87mmol), phosphorus oxychloride 40ml, stirring down, room temperature reaction reacted completely in 24 hours.After the cooling, the pressure reducing and steaming phosphorus oxychloride, resistates is slowly poured in the water, and the adularescent solid is separated out under stirring, and with the suspension liquid that the neutralization of 20% sodium hydroxide obtains, suction filtration obtains 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine.
Synthesizing of embodiment 18:3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine
In a round-bottomed bottle, add 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone 2 g (7.87mmol), phosphorus oxychloride 40ml stirs following 50 ℃ of following reactions and reacted completely in 12 hours.After the cooling, the pressure reducing and steaming phosphorus oxychloride, resistates is slowly poured in the water, and the adularescent solid is separated out under stirring, and with the suspension liquid that the neutralization of 20% sodium hydroxide obtains, suction filtration obtains 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine.
Synthesizing of embodiment 19:3-chloro-6-methyl-4-(3-trifluoromethyl)-pyridazine
In a round-bottomed bottle, add 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone 2g (7.87mmol), phosphorus oxychloride 40ml, stirring refluxes down reacted completely in 2 hours.After the cooling, the pressure reducing and steaming phosphorus oxychloride, resistates is slowly poured in the water, the adularescent solid is separated out under stirring, with the suspension liquid that the neutralization of 20% sodium hydroxide obtains, suction filtration, obtain 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine 2.10g, yield 98.1%, mp 125-126 ℃;
1H NMR (300MHz) δ: 2.78 (s, 3H, CH
3), 7.32 (s, 1H, ArH), 7.62-7.78 (m, 4H, 4ArH); Anal:calc for C
12H
8ClF
3N
2C 52.86, and H 2.96, and N 10.27; Found C 52.82, H 3.03, and N 10.04.
Synthesizing of embodiment 20:6-methyl-3-anilino-4-(3-trifluoromethyl) pyridazine
In in the 5ml round-bottomed bottle, add 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine 0.14g (0.5mmol), aniline 0.19g (1.0mmol) is warming up to 50 ℃ of reaction 24h, and the TLC monitoring reaction is complete.The cooling back, concentrates the back and obtains 6-methyl-3-anilino-4-(3-trifluoromethyl) pyridazine direct the separation with column chromatography [V (sherwood oil)/V (ethyl acetate)=2/1] the reaction solution stripping with methylene dichloride.
Synthesizing of embodiment 21:6-methyl-3-anilino-4-(3-trifluoromethyl) pyridazine
In in the 5ml round-bottomed bottle, add 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine 0.14g (0.5mmol), aniline 0.19g (1.0mmol) is warming up to 120 ℃ of reaction 10h, and the TLC monitoring reaction is complete.The cooling back, concentrates the back and obtains 6-methyl-3-anilino-4-(3-trifluoromethyl) pyridazine direct the separation with column chromatography [V (sherwood oil)/V (ethyl acetate)=2/1] the reaction solution stripping with methylene dichloride.
Synthesizing of embodiment 22:6-methyl-3-anilino-4-(3-trifluoromethyl) pyridazine
In in the 5ml round-bottomed bottle, add 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine 0.14g (0.5mmol), aniline 0.19g (1.0mmol) is warming up to 160 ℃ of reaction 4h, and the TLC monitoring reaction is complete.The cooling back, concentrates the back and obtains 6-methyl-3-anilino-4-(3-trifluoromethyl) pyridazine, yield 54.5% direct the separation with column chromatography [V (sherwood oil)/V (ethyl acetate)=2/1] the reaction solution stripping with methylene dichloride.
Synthesized compound (I1-I16) according to similar method, all compounds are through nuclear-magnetism, and 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 | R 4 | Outward appearance | Fusing point/℃ |
| I-1 | CH 3 | H | C 6H 5 | H | Buff powder | 140-141 |
| I-2 | CH 3 | H | 2-CH 3C 6H 4 | H | White powder | 136-137 |
| I-3 | CH 3 | H | 3-CH 3C 6H 4 | H | Buff powder | 118-119 |
| I-4 | CH 3 | H | 4-CH 3C 6H 4 | H | Buff powder | 147-148 |
| I-5 | CH 3 | H | 2，4-(CH 3) 2C 6H 3 | H | Light brown powder | 144-145 |
| I-6 | CH 3 | H | 2-CH 3OC 6H 4 | H | Yellow powder | 156-157 |
| I-7 | CH 3 | H | 3-CH 3OC 6H 4 | H | Yellow powder | 136-137 |
| I-8 | CH 3 | H | 2-FC 6H 4 | H | White powder | 116-117 |
| I-9 | CH 3 | H | 4-FC 6H 4 | H | Yellow powder | 163-164 |
| I-10 | CH 3 | H | 2-ClC 6H 4 | H | Light brown powder | 98-99 |
| I-11 | CH 3 | H | 3-ClC 6H 4 | H | Light brown powder | 139-140 |
| I-12 | CH 3 | H | 4-ClC 6H 4 | H | Buff powder | 164-166 |
| I-13 | CH 3 | H | 2-BrC 6H 4 | H | Yellow powder | 147-148 |
| I-14 | CH 3 | H | 4-BrC 6H 4 | H | Buff powder | 175-176 |
| I-15 | CH 3 | H | 3-CF 3C 6H 4 | H | White powder | 113-114 |
| I-16 | CH 3 | H | 4-CF 3C 6H 4 | H | White powder | 148-149 |
Table 2. compound (I)
1H NMR spectrum data
| No (CDCl 3) | 1H NMR |
| I-1 | 2.66(s，3H，CH 3)，6.28(s，1H，NH)，6.98-7.07(m，2H，2ArH)，7.23-7.30 (m，2H，2ArH)，7.55-7.78(m，6H，6ArH) |
| I-2 * | 2.07(s，3H，CH 3)，2.65(s，3H，CH 3)，6.20(s，1H，NH)，6.92-7.16(m，4H， 4ArH)，7.23-7.30(m，2H，2ArH)，7.63-7.75(m，4H，4ArH)，8.02-8.04(d， 1H，J H＝8.0Hz，ArH) |
| I-3 | 2.31(s，3H，CH 3)，2.66(s，3H，CH 3)，6.24(s，1H，NH)，6.81-6.83(d，1H， J H＝7.5Hz，ArH)，7.06(s，1H，ArH)，7.13-7.18(t，1H，J H＝7.8Hz， ArH)，7.29-7.32(d，1H，J H＝7.8Hz，ArH)，7.64-7.77(m，4H，4ArH) |
| I-4 | 2.29(s，3H，CH 3)，2.64(s，3H，CH 3)，6.20(s，1H，NH)，7.04(s，1H，ArH)， 7.07-7.10(d，2H，J H＝8.1Hz，2ArH)，7.43-7.46(d，2H，J H＝8.4Hz， 2ArH)，7.64-7.77(m，4H，4ArH) |
| I-5 | 2.05(s，3H，CH 3)，2.25(s，3H，CH 3)，2.64(s，3H，CH 3)，6.09(s，1H，NH)， |
| 6.93-7.05(m，3H，3ArH)，7.61-7.87(m，5H，5ArH) | |
| I-6 | 2.66(s，3H，CH 3)，3.73(s，3H，CH 3)，6.81-7.07(m，4H，4ArH)，7.35(s， 1H，NH)，7.69-7.83(m，4H，4ArH)，8.82-8.86(m，1H，ArH) |
| I-7 | 2.63(s，3H，CH 3)，3.78(s，3H，CH 3)，6.13(s，1H，NH)，6.81-6.84(d，2H， J H＝9.0Hz，2ArH)，7.03(s，1H，ArH)，7.43-7.46(d，2H，J H＝9.0Hz， 2ArH)，7.66-7.76(m，4H，4ArH) |
| I-8 | 2.68(s，3H，CH 3)，6.67(s，1H，NH)，6.93-7.19(m，4H，4ArH)，7.72-7.76 (m，4H，4ArH)，8.66-8.71(m，1H，ArH) |
| I-9 | 2.65(s，3H，CH 3)，6.20(s，1H，NH)，6.95-7.06(m，3H，3ArH)，7.49-7.54 (m，2H，2ArH)，7.68-7.79(m，4H，4ArH) |
| I-10 * | 2.68(s，3H，CH 3)，6.90-8.86(m，10H，9ArH+NH) |
| I-11 | 2.67(s，3H，CH 3)，6.31(s，1H，NH)，6.95-7.41(m，4H，4ArH)，7.68-7.79 (m，5H，5ArH) |
| I-12 | 2.66(s，3H，CH 3)，6.27(s，1H，NH)，7.08(s，1H，ArH)，7.22-7.25(d，2H， J H＝9.0Hz，2ArH)，7.53-7.56(d，2H，J H＝8.7Hz，2ArH)，7.68-7.80(m， 4H，4ArH) |
| I-13 | 2.68(s，3H，CH 3)，6.28(s，1H，NH)，7.10-7.14(m，3H，3ArH)，7.46-7.50 (m，1H，ArH)，7.68-7.82(m，5H，5ArH) |
| I-14 | 2.66(s，3H，CH 3)，6.26(s，1H，NH)，7.08(s，1H，ArH)，7.37-7.40(d，2H， J H＝9.0Hz，2ArH)，7.49-7.52(d，2H，J H＝9.0Hz，2ArH)，7.67-7.80(m， 4H，4ArH) |
| I-15 | 2.68(s，3H，CH 3)，6.42(s，1H，NH)，7.12(s，1H，ArH)，7.23-7.26(d，1H， J H＝7.5Hz，ArH)，7.36-7.41(t，1H，J H＝8.1Hz，ArH)，7.69-7.83(m，6H， 6ArH) |
| I-16 | 2.67(s，3H，CH 3)，6.29(s，1H，NH)，7.09(s，1H，ArH)，7.12-7.15(d，2H， J H＝8.4Hz，2ArH)，7.58-7.61(d，2H，J H＝9.0Hz，2ArH)，7.68-7.80(m， 4H，4ArH) |
*Be 400MHz, default to 300MHz
The primary dcreening operation of embodiment 23, application---weeding activity is measured
Duckweed experimental technique: duckweed is cultivated in the DATKO nutrient solution, changed nutrient solution weekly one time, to obtain vigorous, the consistent plant of growth.According to the solvability of test compound, use the organic solvent dissolution compound, then with solution point on filter paper, treat organic solvent volatilization after, filter paper is put into culturing bottle.Add the 15ml nutrient solution in culturing bottle, vibration inserts 10 thalluses more than 10 minutes then, and cultivates down in long day condition (16h/8h).Observe every day thallophytic growth be subjected to the inhibition situation, cultivate after 7 days, measure and write down the variation of fresh weight, dry weight and chlorophyll content and the color etc. of each experimental group duckweed.
Chlorophyll in the plant, is got supernatant liquor after centrifugal and is measured 665nm and 649nm OD value down 4 ℃ of extractions with 96% ethanol, and chlorophyll content is with following formula calculating:
Chl content＝(6.10A665nm+20.04A649nm)×total volume of extract/FW(μg/g)
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 cauline leaf spraying to the certain period with doses when seedling length handles.Handle 30 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): in the plastics cuvette of diameter 8cm, put into a certain amount of soil, add a certain amount of water, after planting cover certain thickness soil, and the same day with the doses dispenser, in greenhouse, cultivate then, come up before with plastic covered.After emerging, every day in addition quantitative clear water to keep normal growth.Handle 30 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%;-: 0%
The herbicidal effect of table 3 target compound (duckweed method)
| Numbering | Fresh weight inhibiting rate (%) | Chlorophyll inhibiting rate (%) | ||
| 10μgml -1 | 1μgml -1 | 10μgml -1 | 1μgml -1 | |
| I-1 | 75 | 72 | 100 | 100 |
| I-2 | 54 | 34 | 83 | 65 |
| I-3 | 44 | 43 | 100 | 100 |
| I-4 | 62 | 40 | 96 | 95 |
| I-5 | 57 | 39 | 72 | 69 |
| I-6 | 0 | 0 | 82 | 62 |
| I-7 | 57 | 19 | 100 | 100 |
| I-9 | 33 | 29 | 100 | 100 |
| I-11 | 32 | 28 | 100 | 100 |
| I-12 | 46 | 22 | 100 | 82 |
| I-13 | 37 | 0 | 100 | 100 |
| I-14 | 44 | 32 | 100 | 87 |
| I-15 | 52 | 51 | 100 | 100 |
| I-16 | 47 | 31 | 63 | 59 |
| Diflufenican | 64 | 57 | 94 | 90 |
Table 4: the weeding activity inhibiting rate (%) of part of compounds (I) (dosage 750 gram/hectares)
| Numbering | Rape | Three-coloured amaranth | The barnyard grass grass | Lady's-grass | ||||
| Soil treatment | Cauline leaf is handled | Soil treatment | Cauline leaf is handled | Soil treatment | Cauline leaf is handled | Soil treatment | Cauline leaf is handled | |
| I-1 | +++ | +++++ * | ++ | ++++ * | +++ * | + | +++ * | - |
| I-2 | + | +++++ * | - | ++ | - | + | + | + |
| 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 | - | +++ | ++ | ++ | - | ++ | + | ++ |
| Diflufenican | ++++ * | +++++ * | +++++ * | +++++ * | +++++ * | ++++ * | +++++ * | +++++ * |
*: the blade that grows after the chemicals treatment all is a white
+++++：≥80％；++++：60～79％；+++：40～59％；++：20～39％；+：≤19％；-：0％
Table 5: the weeding activity inhibiting rate (%) of part of compounds (I) (cauline leaf processing)
| Numbering | Treatment dosage (gram/mu) | Rape | Three-coloured amaranth | Numbering | Treatment dosage (gram/mu) | Rape | Three-coloured amaranth |
| I-1 | 40 20 10 5 | +++++ *+++++ *++++ *++++ * | ++++ * +++ * +++ * + | I-12 | 40 20 10 5 | +++++ * +++++ * +++++ * +++ * | ++++ * ++++ * +++ * +++ * |
| I-9 | 40 20 10 5 | +++++ *+++++ *+++ *+++ * | ++++ * +++ * +++ * ++ | I-15 | 40 20 10 5 | +++++ * ++++ * ++++ * +++ * | +++ * +++ * ++ ++ |
| Diflufenican | 40 20 10 5 | +++++ *+++++ *+++++ *+++ * | +++++ * ++++ * ++++ * +++ * |
*: the blade that grows after the chemicals treatment all is a white
Claims (4)
1, a kind of 3-substituted-amino pyridazine compound with weeding activity is characterized in that the general formula of this compounds is (I):
Wherein,
R
1, 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: 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;
R
4: H, alkyl;
R
5: H, alkyl, haloalkyl;
R
6, R
7: 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, compound according to claim 1 is characterized in that:
Said R
1, R
2Be hydrogen, methyl, trifluoromethyl, chlorine, bromine, methoxyl group, oxyethyl group, methylamino-, dimethylamino, phenyl;
R
3It is phenyl, the 2-fluorophenyl, the 3-fluorophenyl, the 4-fluorophenyl, 2, the 3-difluorophenyl, 2, the 4-difluorophenyl, 2, the 5-difluorophenyl, 2, the 6-difluorophenyl, 3, the 4-difluorophenyl, 3, the 5-difluorophenyl, the 2-cyano-phenyl, the 3-cyano-phenyl, the 4-cyano-phenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, 2, the 3-dichlorophenyl, 2, the 4-dichlorophenyl, 2, the 5-dichlorophenyl, 2, the 6-dichlorophenyl, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, the 2-bromophenyl, the 3-bromophenyl, the 4-bromophenyl, 2, the 3-dibromo phenyl, 2, the 4-dibromo phenyl, 2, the 5-dibromo phenyl, 2, the 6-dibromo phenyl, 3, the 4-dibromo phenyl, 3, the 5-dibromo phenyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, 2, the 4-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 3, the 5-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, the 2-trifluoromethyl, the 3-trifluoromethyl, the 4-trifluoromethyl, the 4-Trifluoromethoxyphen-l, the 4-tert-butyl-phenyl, the 2-phenyl;
R
4Be hydrogen, methyl.
3, the preparation method of the described compound of a kind of claim 1 is characterized in that it is to finish through following step:
(1) be 1: 1～2 to mix in molar ratio with 3-trifluoromethyl phenylacetic acid and dehydrated alcohol, under making solvent, benzene reacts, add 100～300ml benzene solvent in every mole of 3-trifluoromethyl phenylacetic acid reactant, and the vitriol oil that adds 0.5～2 times of amount dewaters, heat 40～120 ℃, 6～48 hours, anhydrate with the water trap branch; After reaction finishes reaction solution is poured in the water, be neutralized to neutrality, isolate oil reservoir, the water layer extracted with diethyl ether merges organic layer, and drying is filtered, boil off solvent after, underpressure distillation, 116～120 ℃/18mmHg of collection cut obtains 3-trifluoromethyl phenylacetic acid ethyl ester;
(2) in carbon tetrachloride solvent, the 3-trifluoromethyl phenylacetic acid ethyl ester that the step makes in the adding, and N-bromosuccinimide (NBS), mol ratio is 1: 1～2, and drip 48% hydrobromic acid solution initiation reaction, reacted 2～48 hours down at 0～150 ℃, wherein, add 500～2000ml carbon tetrachloride solvent in every mole of 3-trifluoromethyl phenylacetic acid ethyl ester and add the 1ml hydrobromic acid solution; Reaction after finishing is removed the solid filtering in the reaction solution, after solvent is sloughed in decompression, obtains colourless transparent liquid, is bromo-3-trifluoromethyl ethyl acetate;
(3) in acetone solvent, the step makes in the adding bromo-3-trifluoromethyl ethyl acetate, methyl aceto acetate and Anhydrous potassium carbonate powder, mol ratio is 1: 1～2: 1～3, react 0.5～8 hour down to reacting completely at 0～100 ℃, wherein, add 1000～3000ml acetone solvent in every mole bromine generation-3-trifluoromethyl ethyl acetate; After reaction solution is sloughed solvent, use dichloromethane extraction, extraction liquid saturated common salt water washing, drying after solvent is sloughed in decompression, obtains the crude product of 2-ethanoyl-3-(3-trifluoromethyl)-diethyl succinate, can be directly used in next step reaction;
(4) go up and to add 40% NaOH solution in the crude product of 2-ethanoyl-3-(3-trifluoromethyl)-diethyl succinate that the step makes, mol ratio is 1: 3～7, stirs down 0～100 ℃ of reaction 1～8 hour down, and reaction adds hcl acidifying; Reaction solution after the acidifying was 0～100 ℃ of reaction 1～10 hour, and the reaction solution organic solvent extraction filters, and is spin-dried for, and obtains the crude product of 4-oxo-2-(3-trifluoromethyl)-valeric acid, can be directly used in next step reaction;
(5) in alcohol solvent, the crude product and 85% hydrazine hydrate solution of 4-oxo-2-(3-trifluoromethyl)-valeric acid that the step makes in the adding, mol ratio is 1: 1～3,0～80 ℃ was reacted 1～10 hour, wherein, every mole of 4-oxo-2-(3-trifluoromethyl)-valeric acid adds 500～3000ml alcohol solvent; Reaction solution is poured in the water, had light yellow solid to separate out, filter out solid, drying obtains 6-methyl-4-(3-trifluoromethyl)-4,5-dihydro-3 (2H) pyridazinone;
(6) in dimethyl sulfoxide solvent, 6-methyl-4-(3-trifluoromethyl)-4 that the step makes in the adding, 5-dihydro-3 (2H) pyridazinone and Anhydrous potassium carbonate powder, mol ratio is 1: 1～5,0～80 ℃ was reacted 1～48 hour down, wherein, every mole of 6-methyl-4-(3-trifluoromethyl)-4 adds 3000～4000ml dimethyl sulfoxide solvent in 5-dihydro-3 (2H) pyridazinone; Reactant is poured in the water, with dilute hydrochloric acid neutralization, solvent extraction, washing, drying, slough solvent after, obtain 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone;
(7) in the phosphorus oxychloride solvent, 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone that the step makes in the adding, stirred 0.5～24 hour in the time of 0～100 ℃, boil off unnecessary phosphorus oxychloride, resistates is poured in the water, and suction filtration gets white solid, is 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine, wherein, add 5000～6000ml phosphorus oxychloride solvent in every mole of 6-methyl-4-(3-trifluoromethyl)-3 (2H) pyridazinone;
(8) go up 3-chloro-6-methyl-4-(3-trifluoromethyl) pyridazine and the substituted aniline Hybrid Heating that the step makes, mol ratio is 1: 1～10; Mixture is 50～220 ℃ of reactions 1～24 hour, after the cooling, with organic solvent with the reaction solution stripping, washing, drying is filtered, and directly uses column chromatography after concentrated and obtains 3-substituted-amino-6-methyl-4-(3-trifluoromethyl) pyridazine.
4, the described application of compound of a kind of claim 1 is characterized in that, as bleaching herbicide, can be used for preventing and kill off broadleaf weeds and gramineous weeds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100575649A CN100569756C (en) | 2007-06-06 | 2007-06-06 | Has 3-substituted-amino pyridazine class derivative of weeding activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100575649A CN100569756C (en) | 2007-06-06 | 2007-06-06 | Has 3-substituted-amino pyridazine class derivative of weeding activity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058563A true CN101058563A (en) | 2007-10-24 |
| CN100569756C CN100569756C (en) | 2009-12-16 |
Family
ID=38864883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100575649A Expired - Fee Related CN100569756C (en) | 2007-06-06 | 2007-06-06 | Has 3-substituted-amino pyridazine class derivative of weeding activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100569756C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718700A (en) * | 2012-07-10 | 2012-10-10 | 南开大学 | Study on preparation and application of 3, 5, 6-trichlorine-2-pyridyloxyacetic acid derivatives |
| CN109053693A (en) * | 2018-09-20 | 2018-12-21 | 周银平 | The preparation and its application of pyridazine aminated compounds |
| CN115819354A (en) * | 2022-12-13 | 2023-03-21 | 杭州澳赛诺生物科技有限公司 | Synthesis method of alkyl-substituted 6-alkyl-4-aminopyridazine or salt thereof |
-
2007
- 2007-06-06 CN CNB2007100575649A patent/CN100569756C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718700A (en) * | 2012-07-10 | 2012-10-10 | 南开大学 | Study on preparation and application of 3, 5, 6-trichlorine-2-pyridyloxyacetic acid derivatives |
| CN102718700B (en) * | 2012-07-10 | 2016-03-23 | 南开大学 | 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative preparations and applicatio is studied |
| CN109053693A (en) * | 2018-09-20 | 2018-12-21 | 周银平 | The preparation and its application of pyridazine aminated compounds |
| WO2020057391A1 (en) * | 2018-09-20 | 2020-03-26 | 周银平 | Preparation of pyridazinyl amine compound and application thereof |
| CN109053693B (en) * | 2018-09-20 | 2021-02-05 | 顺毅股份有限公司 | Preparation and application of pyridazine amine compound |
| CN115819354A (en) * | 2022-12-13 | 2023-03-21 | 杭州澳赛诺生物科技有限公司 | Synthesis method of alkyl-substituted 6-alkyl-4-aminopyridazine or salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100569756C (en) | 2009-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102869256B (en) | Catechol O-methyltransferase inhibitor and the purposes in treatment mental disorder thereof | |
| JP2598540B2 (en) | Alkoxy-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamides, their preparation and intermediates | |
| CN1293058C (en) | O-cyclopropyl-carboxanilides and their use as fungicides | |
| CN103819413B (en) | The pentadienone compounds of Quinazolinone-containing aryloxy and preparation method and application | |
| JPS61500069A (en) | Herbicidal -aryl-4-substituted-1,4-dihydro-5H-tetrazol-5-ones and their sulfur congeners | |
| CN102311399A (en) | Triazole alcohol antifungal compounds with nitrogen-containing side chains, preparation method thereof and application thereof | |
| RU2670439C2 (en) | Substituted pyrazolyl pyrazole derivative and use thereof as herbicide | |
| JP2002521001A (en) | Cycloimide-substituted benzo-fused heterocyclic herbicides | |
| CN108358896B (en) | Compound for preparing medicine for preventing and treating crop pathogenic bacteria and preparation method | |
| CN110526863B (en) | Acyl thiourea or acyl urea derivative containing trifluoromethylpyridine and application thereof | |
| CN104672162A (en) | Preparation method and use of pentadiene ketone compound containing 1,3,4-oxadiazole sulfo-ethyoxyl | |
| CN101058563A (en) | 3-substituted amidopyridazine derivative with weeding activity and preparation method thereof | |
| LU81779A1 (en) | 1-THIA-3-AZA-4-ONES SUBSTITUTED, THEIR PREPARATION AND THEIR USE IN AGRICULTURE | |
| JP6228667B2 (en) | Novel antifungal oxodihydropyridine carbohydrazide derivatives | |
| CN108059629B (en) | Pyrimidine-containing substituted pyrazole compound and preparation method and application thereof | |
| CN110963973B (en) | Triketone compound containing quinazoline diketone fragment, preparation method and application thereof, and herbicide | |
| CN1962642A (en) | Trifluoromethylphenylpyridazine derivative and its preparation method | |
| CN106543139B (en) | Triazolone compound and application thereof | |
| CN101058562B (en) | 3-substituted oxypyridazine derivative with weeding activity and preparation method thereof | |
| CN104628726A (en) | Synthesis method and application of purine-containing pentadienone derivatives | |
| CN1317265C (en) | Cyanoacrylate derivatives and their preparation method and biological activity | |
| CN102150670B (en) | Application of phenanthroindolizidine and phenanthroquinolizidine derivatives and salts thereof in pesticides | |
| CN103539716A (en) | One group of 2-para chlorphenyl-4-substituted methyl-5- trifluoromethyl-3-cyanpyrrole compounds | |
| CN101648914A (en) | Method for preparing 6-methyl-3-(3,4-dichloroanilino)-4-(3-trifluoromethylphenyl)pyridazine and phytocidal activity thereof | |
| CN105837491B (en) | A kind of novel carboxamide derivative fungicide and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091216 Termination date: 20100606 |