CN1140515C - 3-(2-fluo-4,5,6-substituted phenyl)-1,3-quinazoline-2,4-dione compound with herbiciding activity - Google Patents
3-(2-fluo-4,5,6-substituted phenyl)-1,3-quinazoline-2,4-dione compound with herbiciding activity Download PDFInfo
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- CN1140515C CN1140515C CNB001233483A CN00123348A CN1140515C CN 1140515 C CN1140515 C CN 1140515C CN B001233483 A CNB001233483 A CN B001233483A CN 00123348 A CN00123348 A CN 00123348A CN 1140515 C CN1140515 C CN 1140515C
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Abstract
The present invention relates to a 3-(2-fluo-4, 5, 6-substituted phenyl)-1, 3-quinazoline-2, 4-dione compound with herbicidal activity, which has a general formula (I), wherein R1 is H, halogen, alkyl, alkylogen, alkoxy groups, nitryl and CN; R2 is H, CN, alkyl, alkylogen, alkoxyalkyl, cyanoalkyl, naphthenic bases, alkenyl, alkynyl, carbalkoxy, alkylthio groups, alkylthioalkyl and alkoxycarbonylalkyl; X1 is halogen, alkyl, alkylogen, alkoxy groups, nitryl and CN; X2 is H, halogen, alkyl, alkylogen, naphthenic bases, alkoxy groups, cycloalkoxy, alkenyloxy, alkynyloxy, carbalkoxy, carbalkoxyalkoxyl and carbalkoxyalkylthio groups; X3 is H, halogen, alkyl, alkylogen, alkoxy groups, nitryl and CN; X1 and X2, and X2 and X3 can form benzo 5-or 6-element heterocycles.
Description
The invention belongs to the weedicide field.
Because weedicide or its composition are in use for some time, weeds can produce resistance to it, therefore, need constantly invention novel with improved herbicidal compound and composition.In addition, consider the factor of aspects such as energy economy ﹠ environment, the invention weedicide different with existing herbicide action mechanism also is very important.
Some 3-(2-fluorine substituted-phenyl)-1,3-quinazoline-2, the 4-cyclohexadione compounds is seen EP40793, U54405623 as the existing report of medicine.But in above-mentioned patent, do not see the report of its weeding activity.And 3-shown in the present (2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds are not also seen open.
The object of the present invention is to provide a kind of new 3-(2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds; Another object of the present invention is this compounds and composition thereof to use, to control effectively single broadleaf weed as broad-spectrum herbicide behind Miao Qianmiao.The present invention also relates to these compounds of preparation, uses the method that these compounds and composition thereof carry out weeding.
The general formula of compound provided by the present invention is as follows:
Wherein:
R
1Be H, halogen, (C
1-C
4) alkyl, halo (C
1-C
3) alkyl, (C
1-C
3) alkoxyl group, halo (C
1-C
3) alkoxyl group, nitro or CN;
R
2Be H, CN, (C
1-C
4) alkyl, halo (C
1-C
3) alkyl, (C
1-C
4) alcoxyl (C
1-C
2) alkyl, (C
2-C
4) alkene oxygen (C
1-C
2) alkyl, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl, cyanogen (C
1-C
4) alkyl, (C
1-C
6) cycloalkyl, (C
3-C
6) thiazolinyl, halo (C
3-C
6) thiazolinyl, (C
3-C
6) alkynyl, halo (C
3-C
6) alkynyl, (C
1-C
4) carbalkoxy, (C
1-C
4) alkyl sulphonyl, (C
1-C
3) alkyl sulfonyl (C
1-C
2) alkyl base or (C
1-C
4) carbalkoxy (C
1-C
2) alkyl;
X
1Be halogen, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, nitro or CN;
X
2Be H, halogen, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
1-C
6) cycloalkyl, (C
1-C
6) alkoxyl group, (C
3-C
6) cycloalkyloxy, (C
2-C
6) alkene oxygen base, (C
3-C
6) alkynyloxy group, (C
1-C
4) carbalkoxy, (C
2-C
6) alkenyloxycarbonyl, (C
3-C
6) alkynes oxygen carbonyl, (C
1-C
6) alkyl sulfonyl amino, (C
1-C
6) alkyl sulfonyl (C
1-C
2) alkylamino, (C
1-C
4) carbalkoxy (C
1-C
2) alkoxyl group or (C
1-C
4) carbalkoxy (C
1-C
2) alkylthio;
X
3Be H, halogen, (C
1-C
4) alkyl, halo (C
1-C
3) alkyl, (C
1-C
3) alkoxyl group, nitro or CN;
Work as X
3During for H, X
1And X
2Can form benzo 5-as follows or 6-unit heterocycle:
Or
Wherein:
L is O or S;
R
3Be H or (C
1-C
4) alkyl;
R
4Be H, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
1-C
6) cycloalkyl, (C
3-C
6) thiazolinyl, halo (C
3-C
6) thiazolinyl, (C
3-C
6) alkynyl, halo (C
3-C
6) alkynyl, (C
1-C
6) alcoxyl (C
1-C
2) alkyl, (C
2-C
6) alkene oxygen (C
1-C
2) alkyl, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl or cyanogen (C
1-C
6) alkyl;
R
5Be H, fluorine or (C
1-C
3) alkyl;
Work as X
1During for CN or halogen, X
2And X
3Can form benzo 5-unit heterocycle as follows:
Or
Wherein,
Y is O, S or-NR
9
Y, for Y or-CO;
R
6, R
7, R
8Be H, halogen, CN, (C
1-C
6) alkyl, (C
3-C
6) cycloalkyl, (C
2-C
6) thiazolinyl, (C
3-C
6) alkynyl, halo (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, (C
1-C
6) hydroxyalkyl ,-CO
2R
10, aldehyde radical, (C
1-C
6) alkyl carbonyl, (C
1-C
6) alkylthio, (C
1-C
6) alkyl sulphinyl, (C
1-C
6) alkyl sulphonyl, halo (C
1-C
6) alkylthio, halo (C
1-C
6) alkyl sulphonyl or halo (C
1-C
6) alkyl sulphinyl;
R
9, R
10Be respectively H, (C
1-C
6) alkyl, (C
3-C
6) thiazolinyl or (C
3-C
6) alkynyl; And its esters preparation.
Comparatively preferred compound is among the present invention, in the represented compound of general formula (I):
R
1Be H;
R
2Be H, CN, (C
1-C
4) alkyl, halo (C
1-C
3) alkyl, (C
1-C
4) alcoxyl (C
1-C
2) alkyl, cyanogen (C
1-C
4) alkyl, (C
1-C
6) cycloalkyl, (C
3-C
6) thiazolinyl, (C
3-C
6) alkynyl, (C
1-C
3) alkyl sulfonyl (C
1-C
2) alkyl base or (C
1-C
4) carbalkoxy (C
1-C
2) alkyl;
X
1Be halogen, halo (C
1-C
6) alkyl, nitro or CN;
X
2Be halogen, halo (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, (C
3-C
6) cycloalkyloxy, (C
2-C
6) alkene oxygen base, (C
3-C
6) alkynyloxy group, (C
1-C
4) carbalkoxy, (C
2-C
6) alkenyloxycarbonyl, (C
3-C
6) alkynes oxygen carbonyl, (C
1-C
6) alkyl sulfonyl amino, (C
1-C
6) alkyl sulfonyl (C
1-C
2) alkylamino or (C
1-C
4) carbalkoxy (C
1-C
2) alkoxyl group;
X
3Be H;
X
1And X
2Can also form benzo 5-as follows or 6-unit heterocycle:
Or
Wherein:
L is O;
R
3Be H or (C
1-C
3) alkyl;
R
4Be (C
1-C
5) alkyl, halo (C
1-C
5) alkyl, (C
1-C
5) cycloalkyl, (C
3-C
5) thiazolinyl, halo (C
3-C
5) thiazolinyl, (C
3-C
5) alkynyl, halo (C
3-C
5) alkynyl, (C
1-C
4) alcoxyl (C
1-C
2) alkyl, (C
2-C
5) alkene oxygen (C
1-C
2) alkyl, (C
3-C
5) alkynes oxygen (C
1-C
2) alkyl or cyanogen (C
1-C
5) alkyl; R
5Be H, fluorine or (C
1-C
3) alkyl;
And its esters preparation.
Preferred compound is following two portions compound among the present invention, and first part is in the compound shown in the general formula (I):
R
1And X
3Be H;
X
1Be halogen, halo (C
1-C
5) alkyl, nitro or CN;
R
2Be H, CN, (C
1-C
4) alkyl, halo (C
1-C
3) alkyl, (C
1-C
4) alcoxyl (C
1-C
2) alkyl, cyanogen (C
1-C
4) alkyl, (C
1-C
6) cycloalkyl, (C
3-C
6) thiazolinyl, (C
3-C
6) alkynyl or (C
1-C
4) carbalkoxy (C
1-C
2) alkyl;
X
2Be halogen, halo (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, (C
3-C
6) cycloalkyloxy, (C
2-C
6) alkene oxygen base, (C
3-C
6) alkynyloxy group, (C
1-C
4) carbalkoxy, (C
2-C
6) alkenyloxycarbonyl, (C
3-C
6) alkynes oxygen carbonyl or (C
1-C
4) carbalkoxy (C
1-C
2) alkoxyl group;
And its esters preparation.
The second section compound is for working as R
1, X
3During for H, X
1And X
2Can form benzo 6-unit heterocycle as follows:
Wherein:
R
2Be H, CN, (C
1-C
4) alkyl, halo (C
1-C
3) alkyl, (C
1-C
4) alcoxyl (C
1-C
2) alkyl, cyanogen (C
1-C
4) alkyl or (C
1-C
6) cycloalkyl;
R
4Be (C
1-C
5) alkyl, halo (C
1-C
5) alkyl, (C
1-C
5) cycloalkyl, (C
3-C
5) thiazolinyl, halo (C
3-C
5) thiazolinyl, (C
3-C
5) alkynyl, halo (C
3-C
5) alkynyl, (C
1-C
4) alcoxyl (C
1-C
2) alkyl, (C
2-C
5) alkene oxygen (C
1-C
2) alkyl, (C
3-C
5) alkynes oxygen (C
1-C
2) alkyl or cyanogen (C
1-C
5) alkyl;
And its esters preparation.
The salt preparation of The compounds of this invention can be by The compounds of this invention and organic acid such as acetate, mineral acid example hydrochloric acid and metal-salt thereof (as zinc chloride or iron(ic) chloride) mix formation.
So-called alkyl is meant the straight or branched form, for example groups such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl.Cycloalkyl is meant and comprises the closed chain form, for example groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.Alkylhalide group is meant the group that alkyl is replaced by one or more halogen atoms.The alkyl sulfonyl alkyl refers to alkyl sulphonyl (alkyl-SO on the alkyl
2) substituted radical, as groups such as sulfonyloxy methyl methyl.The alkyl sulfenyl alkyl refers to alkyl sulphinyl on the alkyl (substituted radical of alkyl-SO) is as groups such as methyl sulfinyl methyl.
So-called thiazolinyl is meant the straight or branched form, the group of 1 to 2 carbon-carbon double bond is arranged, for example vinyl, propenyl, allyl group etc.
So-called alkynyl is meant the straight or branched form, and 1 to 2 carbon carbon triple-linked group, for example ethynyl, proyl, propargyl etc. are arranged.
So-called alkoxyl group is meant the straight or branched form, and end is connected with the group of Sauerstoffatom, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, tert-butoxy etc.
So-called alkylthio is meant the straight or branched form, and end is connected with the group of sulphur atom, for example methylthio group, ethylmercapto group etc.
So-called halogen is meant fluorine, chlorine, bromine, iodine.
General formula compound of the present invention (I) can be prepared by following method:
Benzoyl chloride (II) and aniline (III) are in The suitable solvent, and temperature made intermediate (IV) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.Solvent can be chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.Can add alkaloids under some situation, as triethylamine, pyridine, sodium hydroxide, oxygen potassium oxide, yellow soda ash, salt of wormwood, sodium bicarbonate etc.
Aniline (III) can for example be prepared by currently known methods; Can be by the substituted-nitrobenzene that buys on the market or can make by currently known methods, with reductive agent such as iron, zinc, reactions such as titanium or hydrogen (referring to the method for describing among the patent EPA0083055A2), in The suitable solvent, temperature made to the following reaction of boiling point for-10 ℃ in 0.5-48 hour.Solvent can be water, acetate, and acetone, chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, ethanol, DMF, THF or dioxane, and by mixed solvent of above-mentioned two or three solvent composition etc.
Intermediate (V) can obtain with reference to the preparation method of aniline.
Intermediate (V) and phosgene or ClCO
2CH
3In The suitable solvent ,-10 ℃ to boiling point down reaction made target compound (VI) in 0.5-48 hour.Solvent can be chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.Can add alkaloids under some situation, as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate etc.
Intermediate (VI) and haloalkane or alkyl sulfonate esters are under alkaline condition, and in The suitable solvent, temperature made compound (I) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.Solvent can be acetone, chloroform, and methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc., alkali is triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and sodium hydride etc.
Table 1, table 2 and table 3 are listed the The compounds of this invention of part shown in general formula I.
The The compounds of this invention of table 1 part shown in general formula (I)
| Compound | R 2 | X 1 | X 2 | X 3 | Mp(℃) |
| 1 | H | Cl | H | H | 230-232 |
| 2 | CH 3 | Cl | H | H | 181-182 |
| 3 | CO 2C 2H 5 | Cl | H | H | Oil * |
| 4 | CH 2CO 2C 2H 5 | Cl | H | H | Oil * * |
| 5 | CH 2OC 2H 5 | Cl | H | H | 103-105 |
| 6 | Propargyl | Cl | H | H | 224-225 |
| 7 | C 2H 5 | Cl | H | H | 164-166 |
| 8 | CN | Cl | H | H | ＞250 |
| 9 | H | Cl | OCH 2CO 2C 2H 5 | H | 170-172 |
| 10 | H | Cl | CO 2CH(CH 3) 2 | H | 240-241 |
| 11 | CH 3 | Cl | OCH 2CO 2C 2H 5 | H | 68-71 |
| 12 | CH 3 | Cl | CO 2CH(CH 3) 2 | H | 70-73 |
| 13 | H | Cl | The alkynes propoxy- | H | 179-182 |
| 14 | CH 3 | Cl | The alkynes propoxy- | H | 175-177 |
*：
1H NMR(CDCl
3)：8.35(d，1H)，7.80(t，1H)，7.30(m，4H)，7.10(d，1H)，4.60(q，2H)，1.30(t，3H).
*:
1H NMR (CDCl
3): 8.32 (d, 1H), 7.75 (t, 1H), 7.28 (m, 4H), 7.05 (d, 1H) 4.95 (abq, 2H), 4.25 (q, 2H), 1.30 (t, 3H). the The compounds of this invention of table 2 part shown in general formula I
The The compounds of this invention of table 3 part shown in general formula I
| Compound | R 2 | R 4 | Mp(℃) |
| 15 | H | H | ＞250 |
| 16 | CH 3 | CH 3 | 255 |
| 17 | Propargyl | Propargyl | 238-239 |
| 18 | Propargyl | CH 3 | 254-256 |
| 19 | H | Propargyl | ＞250 |
| 20 | CH 3 | Propargyl | 225 |
| Compound | R 2 | R 4 | Mp(℃) |
| 21 | CH 3 | CH 3 | 254-256 |
The present invention also comprises by a certain 3-that is made up of the compound and the carrier of weeding activity (2-fluoro-4,5,6-substituted-phenyl)-1 shown in the general formula (I), 3-quinazoline-2,4-cyclohexadione compounds herbicidal composition.
Other embodiments of the present invention are method of controlling weeds, this method comprises 3-(the 2-fluoro-4 with compound shown in the general formula of herbicidally effective amount (I) and acceptable carrier composition, 5, the 6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds herbicidal composition impose on the surface of growth medium of the places of described weeds or described weeds or described weeds.
3-of the present invention (2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds and composition thereof can be used as emerge before and emerge the back weedicide.
Compound of the present invention can preparation form be administered on soil or the blade face.This compound is dissolved in the carrier usually or is mixed with preparation so that be easier to disperse when using as weedicide.For example: but these chemicals can be made into wet-milling, emulsifiable concentrate, pulvis, suspension concentrate, smoke substance or missible oil.In these compositions, added a kind of liquid or solid carrier and when needs, can mix suitable tensio-active agent.
Generally, particularly when on leaf, spraying, wish to contain in the composition auxiliary in the actually operating, as wetting agent, spreading agent, dispersion agent, tackiness agent, tackiness agent etc.Be common to this class auxiliary of this area, can be at the JohnW.McCutcheon, the publication Detergents and Emulsifiers of company, Annual.AlluredPublishing Company, Ridgewood, New Jersey finds among the U.S.A..
3-of the present invention (2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds herbicidal composition can be used with the form of herbicide sprays by method commonly used, for example uses traditional heavy body hydraulic atomizing, lower volume hydraulic atomizing, gas blowout mist, air-spraying or dusting.Extent of dilution and consumption will depend on the type of equipment used, the method for using and the weeds that will control, but the comparatively suitable significant quantity of selecting usually is that per hectare 10 restrains 3000 grams, and preferred significant quantity is that per hectare 50 restrains 1500 grams.
3-of the present invention (2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds herbicidal composition can mix with fertilizer before using mutually.Used said 3-(2-fluoro-4,5,6-substituted-phenyl)-1 in-class, 3-quinazoline-2 in the solid fertilizer composition of 4-ketone compounds, can as ammonium sulfate, ammonium nitrate or ammonium phosphate, apply fertilizer or getting fat component with one or more compounds.Said solid chemical compound or solid fertilizer also can mix in mixing equipment, and perhaps they can be combined into granular composition with fertilizer.Fertilizer can use any ratio, but general said 3-(2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2, the ratio of 4-cyclohexadione compounds in its Ru 2006101161 is about 5% to 25%.These compositions have been controlled the growth that does not need plant when fertilizer is provided, promotes required plant growth.Compound of the present invention can exist with the form that group contains thing or preparation.Preparation preparation or method for compositions can be with reference to " pesticide preparation research " (the publishing in 1969) or the chemical progress seriess of books " pesticide preparation " (publishing in 1973) of American Chemical Society's publication.So-called preparation is meant thinner or the solid carrier of dispersion agent and the mixture of liquid vehicle that active ingredient and agrotechnique are suitable for.Carrier is meant to have emulsifying effect, dissemination and diluting effect, do not damage the active ingredient effect and soil, equipment, crop and agricultural environment are not had the composition of influence, also need add auxiliary agent such as tensio-active agent, stablizer, defoamer or antisettling agent sometimes.
So-called composition or formulation example such as the aqueous solution or aqueous dispersions, oil solution or oily dispersion liquid, paste, pulvis, wettable powder, emulsifiable concentrate, granule, attractive substance, smoke substance etc.Wettable powder, emulsifiable concentrate, paste are prepared also dilute with water before use with high density.In these preparations, can contain the liquid or solid carrier and can add tensio-active agent if necessary.
When preparation foliage spray preparation, for example wetting agent, spreader-sticker, dispersion agent, tamanori or thickening material improve result of use to need to add auxiliary agent usually.Auxiliary agent and using method commonly used all have description in many documents.For example " washing composition and emulsifying agent handbook.
In composition of the present invention, the weight percentage of active ingredient is between 0.1-99%.For the suitable weight percentage of the convenience of transporting and preserving between 0.5-90%, weight percentage preferably is between 1-75%.Composition also can compound and the ratio mode of carrier explain.
Common compound of the present invention can be dissolved in for example dilute with water again in acetone, methyl alcohol, ethanol, dimethyl formamide, pyridine or the dimethyl sulfoxide (DMSO) of specific solvent earlier, and its concentration can be 1% to 90% variation, and preferably is 5% to 50%.
Be the preparation emulsifiable concentrate, compound of the present invention is dissolvable in water a kind of or several mixed solvents, adds emulsifying agent again and strengthens the dispersion effect of compound in water.Active ingredient is usually between 10% to 90% in the emulsifiable concentrate.
Be the wettable powder that preparation is suitable for spraying, compound of the present invention can with pressed powder such as clay, inorganic silicate, carbonate and wetting agent, tamanori and or the dispersion agent composition mixture of porphyrize.Active ingredient is usually between 20% to 99%, and is preferably between 45% to 75%.For example typical 50% wettable powder is 50 parts of compounds of the present invention, 45 parts of silicate and 5 parts of sodium lignosulfonates.
The preparation of pulvis is the inert solid powder mixes by compound of the present invention and porphyrize.Suitable pressed powder such as plant powder, silicate, carbonate or clay.One easily method be with the dilution of the pressed powder of porphyrize with wettable powder.Active ingredient is generally between 20% to 80% in the pulvis, is diluted to 1% to 10% working concentration subsequently.
Compound of the present invention both can use separately also can be mixed together use with other known sterilant, sterilant, weedicide, plant-growth regulator or fertilizer etc.
Use for some, can in weedicide of the present invention, add one or more other weedicide, go out this and can produce additional advantage and effect.When using Herbicidal mixtures, employed relative proportion depends on the relative drug effect of this mixture to desire processing plant.When using the mixture of weedicide, employed relative quantity will depend on pending crop and the selectivity degree in the weed control of expection.
Should be clear and definite be, can carry out various conversion and change under the situation of the scope of the invention defined by the claims.
The following example, give birth to that the result is tested in test and form can be used to further specify the present invention, but do not mean that restriction is by the scope of the present invention shown in the claim.
Synthetic embodiment
Example 1, the preparation of compound 19:
The ice-water bath cooling down, (2.04 restrain with the 2-nitrobenzoyl chloride in 10 minutes, 90%, 10mmol) drips of solution with methylene dichloride (20 milliliters) formation joins 7-fluoro-6-amino-4-(N-propargyl)-1,4-benzoxazine-3-ketone (2.2 grams, 10mmol) and triethylamine (1.1 grams 11mmol) in the mixture that forms with methylene dichloride (20 milliliters), stir under the room temperature and spend the night.Reactant mixes water, sodium bicarbonate aqueous solution, saturated common salt solution washing, anhydrous sodium sulfate drying with methylene dichloride (100 milliliters).Slough solvent and obtain 7-fluoro-6-(2-nitro benzoyl) amino-4-(N-propargyl)-1,4-benzoxazine-3-ketone (3.0 grams, productive rate 81%).
The ice-water bath cooling down; (6.5 restrain with zinc powder in 45 minutes; 100mmol) join 7-fluoro-6-(2-nitro benzoyl) amino-4-(N-propargyl)-1 in batches; 4-benzoxazine-3-ketone (3.0 grams; 8.1mmol) with (100 milliliters of 2N ammonium chlorides; 200mmol), in the mixture that THF (80 milliliters) forms, stirred 3 hours under the room temperature.Reaction mixture is poured in the water, removed by filter insoluble solid, solid is used ethyl acetate and washing respectively, and filtrate is used ethyl acetate extraction, water, saturated common salt solution washing, anhydrous sodium sulfate drying.Slough solvent and obtain 7-fluoro-6-(2-amino benzoyl) amino-4-(N-propargyl)-1,4-benzoxazine-3-ketone (2.5 grams, productive rate 92%).
The toluene solution of phosgene (3.0 grams; 20%; 6.0mmol) join 7-fluoro-6-(2-amino benzoyl) amino-4-(N-propargyl)-1; 4-benzoxazine-3-ketone (1.4 grams; 4.0mmol) in the solution that forms with methylene dichloride (30 milliliters); under the ice-water bath; be added dropwise to triethylamine (1.3 grams in 15 minutes; 12mmol) the solution that forms with methylene dichloride (10 milliliters); stirring at room 2 hours; reactant mixes water, sodium bicarbonate aqueous solution, saturated common salt solution washing, anhydrous sodium sulfate drying with methylene dichloride (80 milliliters).Slough solvent and obtain 1-H-3-[7-fluoro-4-(N-propargyl)-1,4-benzoxazine-3-ketone-6-]-1,3-quinazoline-2,4-diketone (1.2 grams, productive rate 82%), fusing point:＞250 ℃.
Example 2, the preparation of compound 20:
Sodium hydride (0.12 gram, 60%, 3mmol) join 1-H-3-[7-fluoro-4-(N-propargyl)-1 under the ice-water bath cooling, 4-benzoxazine-3-ketone-6-]-1,3-quinazoline-2, (0.73 gram is 2mmol) in the solution that forms with DMF (20 milliliters) for the 4-diketone, stir after 10 minutes under the room temperature and add methyl iodide (1 milliliter, excessive).Stir under the room temperature and spend the night.Reaction mixture is mixed water and saturated common salt water washing, anhydrous sodium sulfate drying with 100 milliliters of ethyl acetate.Slough solvent and obtain 1-methyl-3-[7-fluoro-4-(N-propargyl)-1,4-benzoxazine-3-ketone-6-]-1,3-quinazoline-2,4-diketone (0.52 gram, productive rate 68%), fusing point: 225 ℃.
Other compounds can make by above similar method.
Give birth to and survey embodiment
Test before the seedling: after planting carry out, test compound sparges soil surface, handles and is placed on the greenhouse, waters then; Test behind the seedling, seed germination also grew 10-21 days, made the examination material that has a series of growing stages before the processing, selected size, the consistent examination material of growing stage then, handled, and handled to be placed on the greenhouse and to water.The examination material with compound treatment does not compare.
Usually with the former medicine of acetone solution, or the preparation that makes by preceding method with water dissolution.Spray with mobile belt atomizer.The examination material is put in spraying rolling in the cupboard and is with, and mobile shower nozzle is sprayed onto medicament on the examination material with the covering of the fan Sprayable through examination material top, identical on nozzle and the common field spray device.Roll band and will try material and shift out outside the cupboard, place loft drier dry.
Examination material after the spraying drying places the greenhouse.Test is from the top water spray before the seedling, and test is poured water from the bottom and kept 48 hours so that water does not touch the blade face behind the seedling.
Handling the back investigates in 2-3 week.Carry out active classification with 0% (invalid) to 100% (control fully).Inhibiting rate is total effect of various infringements such as chlorosis, withered spot, retarded growth or the calcination of leaf angle, with compare after obtain the result.Partial test the results are shown in Table 4.
Table 4: the weeding activity of compound in the part general formula I
[before the seedling behind (1200 gram/hectare)/seedling (1200 gram/hectare)]
*;--expression is not surveyed.Table 5: weeds title
| Compound | BYG | FOX | MA | TOM | VEL |
| 2 | 0/0 | 90/0 | 0/0 | 0/40 | 0/50 |
| 3 | 0/0 | 0/0 | 0/0 | 0/30 | 0/30 |
| 5 | 0/0 | 50/30 | 0/0 | 0/40 | 0/85 |
| 6 | 0/0 | 0/0 | 0/0 | 0/30 | 0/80 |
| 7 | 0/0 | 0/0 | 0/0 | 0/30 | 0/60 |
| 10 | 0/0 | 95/20 | 0/0 | 0/60 | 0/90 |
| 11 | 0/0 | 0/0 | 0/0 | 0/0 | 0/20 |
| 12 | 0/95 | 0/95 | 0/0 | 0/60 | 0/100 |
| 14 | 85/95 | 80/100 | 40/20 | 100/95 | 90/85 |
| 15 | 0/0 | 0/0 | 0/0 | 0/0 | 0/80 |
| 16 | 0/0 | 80/0 | 80/0 | 80/75 | 20/85 |
| 17 | 0/30 | 100/60 | 20/0 | 90/80 | 20/80 |
| 18 | 60/0 | 90/80 | 95/20 | 95/40 | 85/80 |
| 19 | 60/40 | 100/60 | --* | -- | 80/100 |
| 20 | 95/0 | 100/0 | -- | -- | 100/100 |
| 21 | 0/0 | 0/0 | 0/0 | 0/70 | 0/0 |
| Be called for short | Generic name | Latin name |
| BYG | The barnyard grass grass | Echinochloa crus- galli |
| FOX | Green dog tail | setaria viridis |
| MA | Flower of Aztec Marigold | Tagetes spp |
| TOM | Tomato | Lycopersicon esculentum |
| VEL | Piemarker | Abutilon theophrasti |
Claims (7)
1. a 3-(2-fluoro-4,5,6-substituted-phenyl)-1,3-quinazoline-2,4-cyclohexadione compounds and salt thereof, shown in general formula (I):
Wherein: R
1Be H; R
2Be H, CN, C
1-4Alkyl, C
1-4Alcoxyl C
1-2Alkyl, C
3-6Alkynyl, C
1-4Carbalkoxy or C
1-4Carbalkoxy C
1-2Alkyl; X
1Be halogen; X
2Be H, C
3-6Alkynyloxy group, C
1-4Carbalkoxy or C
1-4Carbalkoxy C
1-2Alkoxyl group; X
3Be H; X
1And X
2Also can form benzo 6-unit heterocycle as follows:
Or
Wherein: L is O or S; R
3Be H or C
1-4Alkyl; R
4Be H, C
1-6Alkyl or C
3-6Alkynyl.
2. compound as claimed in claim 1 and salt thereof is characterized in that:
R
1Be H;
R
2Be H, CN, C
1-2Alkyl, C
1-2Alcoxyl C
1-2Alkyl, C
3Alkynyl, C
1-2Carbalkoxy or C
1-2Carbalkoxy C
1-2Alkyl;
X
1Be chlorine;
X
2Be H, alkynes propoxy-, isopropoxy carbonyl or C
1-2The carbalkoxy methoxyl group;
X
3Be H;
X
1And X
2Also can form benzo 6-unit heterocycle as follows:
Or
Wherein: L is O; R
3Be H; R
4Be H, methyl or C
3Alkynyl.
3. compound as claimed in claim 2 and salt thereof is characterized in that: X
1And X
2Can form benzo 6-unit heterocycle as follows:
Wherein:
R
2, R
4Be respectively H, methyl or propargyl.
4. herbicidal composition, it is characterized in that: said composition comprises the described compound of claim 1 and salt and acceptable carrier, wherein the weight percentage of active ingredient is 0.1-99%.
5. described compound of claim 1 and the application of salt in management of weeds thereof.
6. the application of the described composition of claim 4 in management of weeds.
7. control method for weed for one kind, it is characterized in that: this method comprises the herbicidal composition as claimed in claim 4 of using herbicidally effective amount on growth medium of these weeds or these weeds or place.
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|---|---|---|---|
| CNB001233483A CN1140515C (en) | 2000-11-30 | 2000-11-30 | 3-(2-fluo-4,5,6-substituted phenyl)-1,3-quinazoline-2,4-dione compound with herbiciding activity |
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| CNB001233483A CN1140515C (en) | 2000-11-30 | 2000-11-30 | 3-(2-fluo-4,5,6-substituted phenyl)-1,3-quinazoline-2,4-dione compound with herbiciding activity |
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| CN1140515C true CN1140515C (en) | 2004-03-03 |
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|---|---|---|---|---|
| CN108727367A (en) * | 2017-04-18 | 2018-11-02 | 山东先达农化股份有限公司 | Benzoxazinones containing pyridopyrimidine dione and its preparation method and application and herbicidal composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100344628C (en) * | 2005-03-29 | 2007-10-24 | 沈阳化工研究院 | Pyrazopyrimidinone compounds and use thereof |
| JP2013540113A (en) | 2010-10-01 | 2013-10-31 | ビーエーエスエフ ソシエタス・ヨーロピア | Herbicidal benzoxazinone |
| CN104557739B (en) * | 2013-10-25 | 2016-11-09 | 山东先达农化股份有限公司 | Triketone compound and preparation method and application thereof |
| CN111356693A (en) | 2017-11-23 | 2020-06-30 | 巴斯夫欧洲公司 | Herbicidal phenyl ethers |
| WO2019101513A1 (en) | 2017-11-23 | 2019-05-31 | Basf Se | Herbicidal pyridylethers |
| CN110357860B (en) * | 2018-04-11 | 2020-12-15 | 山东先达农化股份有限公司 | Quinazoline diketone compound and application thereof as well as pesticide herbicide |
| WO2020063981A1 (en) * | 2018-09-29 | 2020-04-02 | 山东先达农化股份有限公司 | Triketone compound, preparation method therefor and use thereof, and herbicide |
| CN110156767B (en) * | 2019-04-12 | 2020-12-11 | 南开大学 | Cycloalkane pyrimidine diketone compound, preparation method and application thereof, and pesticide herbicide |
| CN116082267B (en) * | 2022-12-25 | 2024-10-11 | 浙江工业大学 | 6-Substituted flumioxazin compound as well as preparation method and application thereof |
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2000
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108727367A (en) * | 2017-04-18 | 2018-11-02 | 山东先达农化股份有限公司 | Benzoxazinones containing pyridopyrimidine dione and its preparation method and application and herbicidal composition |
| CN108727367B (en) * | 2017-04-18 | 2021-01-05 | 山东先达农化股份有限公司 | Benzoxazinone compound containing pyridopyrimidinedione, preparation method and application thereof, and herbicide composition |
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