CN1345722A - 3-(substituted phenyl) 1,2,3-benzotriazine-4-ketone compound with weeding activity - Google Patents
3-(substituted phenyl) 1,2,3-benzotriazine-4-ketone compound with weeding activity Download PDFInfo
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- CN1345722A CN1345722A CN 00123023 CN00123023A CN1345722A CN 1345722 A CN1345722 A CN 1345722A CN 00123023 CN00123023 CN 00123023 CN 00123023 A CN00123023 A CN 00123023A CN 1345722 A CN1345722 A CN 1345722A
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Abstract
The present invention relates to a kind of 3 (substituted phenyl) 1,2,3-phentriazine-4-ketone compound. Said invention also provides its general formula.
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-(substituted-phenyl)-1,2,3-benzotriazine-4-ketone compound can be used as medicine and the existing report of sterilant, see DE1271118, DE2012094 and DD241075.But in above-mentioned patent, do not see the report of its weeding activity.And 3-shown in the present (substituted-phenyl)-1,2, the 3-benzotriazine-4-ketone compound is not also seen open.
The invention provides a kind of new 3-(substituted-phenyl)-1,2,3-benzotriazine-4-ketone compound, its composition, acceptable carrier.As broad-spectrum herbicide, behind Miao Qianmiao, use and effectively to control single broadleaf weed.The present invention also relates to these compounds of preparation, uses the method that these compounds carry out weeding.
The general formula of compound provided by the present invention is as follows:
Wherein:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be H, halogen, ethanoyl;
X
2Be H or halogen;
X
3Be halogen, CN, NO
2
X
5Be H or halogen;
X
4Be halogen, (C
1-C
8) alkyl, 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
8) alkyl sulfonyl amino, (C
1-C
8) alkyl sulfonyl (C
1-C
2) alkylamino, (C
1-C
4) carbalkoxy (C
1-C
2) alkoxyl group;
Work as X
1Be halogen or ethanoyl, X
2And X
5During for hydrogen, X
3And X
4Can form benzo 5-as follows or 6-unit heterocycle:
Wherein:
L is O, S;
R
2Be H or (C
1-C
4) alkyl;
R
3Be H, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (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) alkane
Base, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl, cyanogen (C
1-C
6) alkyl, amino or hydroxyl;
R
4Be H, fluorine, (C
1-C
3) alkyl;
Work as X
1, X
3Be halogen, X
2During for hydrogen, X
4And X
5Can form benzo 5-as follows or 6-unit heterocycle:
Wherein:
Y is O, S or-NR
6
Y ' be Y or-CO;
R
5Be H, halogen, (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, CN, (C
1-C
6) hydroxyalkyl ,-CO
2R
8, aldehyde radical, (C
1-C
8) the alkane carbonyl
Base, (C
1-C
6) alkylthio, (C
1-C
6) alkyl sulphinyl, (C
1-C
6) alkyl sulphonyl, halo (C
1-C
6) alkane
Sulfenyl, halo (C
1-C
6) alkyl sulphonyl, halo (C
1-C
6) alkyl sulphinyl, carboxyl;
R
6, R
8Be respectively H, (C
1-C
6) alkyl, (C
3-C
6) thiazolinyl, (C
3-C
6) alkynyl;
R
7Be H, halogen, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
1-C
8) alkyl carbonyl, NO
2
And its esters preparation.
Comparatively preferred compound is the represented compound of general formula I among the present invention, wherein:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be H, halogen, ethanoyl;
X
2Be H;
X
3Be halogen, CN, NO
2
X
5Be H;
X
4Be halogen, (C
1-C
8) alkyl, halo (C
1-C
4) alkyl, (C
1-C
4) 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, (C3-C6) alkynes oxygen carbonyl, (C
1-C
4) carbalkoxy (C
1-C
2) alkoxyl group;
Work as X
1During for halogen, X
3And X
4Can form benzo 5-as follows or 6-unit heterocycle:
Wherein:
L is O, S;
R
2Be H or (C
1-C
4) alkyl;
R
3Be H, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (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) alkane
Base, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl, cyanogen (C
1-C
6) alkyl, amino or hydroxyl;
R
4Be H, fluorine, (C
1-C
3) alkyl;
And its esters preparation.
Preferred compound is the represented compound of following general formula among the present invention
Wherein:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be H, halogen;
L is O, S;
R
2Be H or (C
1-C
3) alkyl;
R
3Be (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
3-C
6) thiazolinyl, halo (C
3-C
6) thiazolinyl, (C3-C6)
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, cyanogen (C
1-C
6) alkyl, amino or hydroxyl; And its esters preparation.Preferred compound is the represented compound of following general formula among the present invention
Wherein:
R
3Be (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
3-C
6) thiazolinyl, halo (C
3-C
6) thiazolinyl, (C3-C6)
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) alkane
Base, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl, cyanogen (C
1-C
6) alkyl, amino or hydroxyl;
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, n-heptyl, n-octyl, n-nonyl, positive decyl.Cycloalkyl is meant and comprises the closed chain form, for example groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group.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:
Method 1:
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, potassium hydroxide, 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 be made by currently known methods, with reductive agent such as iron, zinc, reaction 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) also can be by following prepared in reaction:
Intermediate (VI) and aniline (III) are in The suitable solvent, and temperature made intermediate (VII) 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, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate etc.
Intermediate (VII) is in the mineral acid example hydrochloric acid, or the adding The suitable solvent, and room temperature is reacted down to boiling point and made intermediate (V) in 0.5-48 hour.Solvent can be chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.
Intermediate (V) and nitrous acid are in The suitable solvent, and-10 ℃ are reacted down to boiling point and to make target compound (I) in 0.5-48 hour.Solvent can be water, chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.
Method 2:
Can make the new compound that belongs to general formula I from compound (I-1).For example compound (I-1) and haloalkane or alkyl sulfonate esters are under alkaline condition, and in The suitable solvent, temperature made compound (I-2) 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 and table 2 are listed the The compounds of this invention of part shown in general formula I.
The compounds of this invention of table 1 part as shown in general formula I
Chemical combination R1 X
1 X
2 X
3 X
4 X
5Mp (℃) thing 1 H H H H H H 149-150 2 H F H H H H 140-141 3 H Cl H H H H 116-117 4 H Br H H H H 105-106 5 H I H H H H 148-149 6 H CH3 H H H H 163-164
7 H CF
3 H H H H 143-144
8 H CN H H H H 158-159
9 H CH
3O H H H H 150-151
10 H H F H H H 133-134
11 H H Cl H H H 140-141
12 H H Br H H H 156-157
13 H H I H H H 143-144
14 H H CH
3 H H H 148-149
15 H H CF
3 H H H 134-135
16 H H CN H H H 192-193
17 H H CH
3O H H H 123-124
18 H H H F H H 147-148
19 H H H Cl H H 183-184
20 H H H Br H H 194-195
21 H H H I H H 134-135
22 H H H CH
3 H H 138-139
23 H H H CF
3 H H 231-232
24 H H H CN H H 226-227
25 H H H CH
3O H H 155-156
26 H F H Cl H H 144-145
27 H Cl H Cl H H 125-126
28 H Cl H F H H 174-175
29 H CH
3 H H CH
3 H
30 H CH
3 H CH
3 H H 126-127
31 H H Cl Cl H H 210-211
32 H H Cl H Cl H 219-220
33 H F H F F H 168-169
34 H F H CN F H 203-205
35 H Cl H F CH
3H 157-158 36 H F H Cl cyclopentyloxy H 133-134 37 H F H Cl alkynes propoxyl group H 185-186 38 H F H Cl C2H
5OCOO- H 128-129
39 H F H Cl (CH
3)
2CH
2OCO-H 183-184
40 H F H Cl C
2H
5OCOCH
2O-H 118-120 41 H Cl H Cl alkynes propoxyl group H 151-152 42 8-Cl F H Cl alkynes propoxyl group H 158-160 43 5-CH3F H Cl alkynes propoxyl group H oil 44 7-CF3F H Cl alkynes propoxyl group H 124-125 45 6-A* F H Cl H H 153-154 46 H F H F H F 173-174 47 H Cl H Cl H Cl 126-127 48 H Br H Br H Br 128-129 *: A=The compounds of this invention of table 2 part as shown in general formula I
No R
1 R
3 mp(℃)
49 H H ＞252
50 H CH
3 255-257
51 H C
2H
5 222-224
52 H NCCH
2 240-242
53 H FCH
2CH
2 215-217
54 H CF
3CH
2 243-245
55 H ClCH
2CH
2 190-192
56 H BrCH
2CH
2 219-220
57 H CH
3OCH
2 213-215
58 H CH
3SCH
2 204-207
59 H CH
3CH
2CH
2174-176 60 H pi-allyl 212-214 61 H 2-chlorallyl 195-197 62 H propargyl 246-248 63 H CH3CH(CN) 165-170
64 H FCH
2CH
2CH
2 184-186
65 H ClCH
2CH
2CH
2 129-131
66 H CHF
2CF
2CH
2 195-197
67 H CH
3OCH
2CH
2 196-199
68 H CH
3CH
20CH
2 178-180
69 H CH
3CH
2CH
2CH
2 160-162
70 H (CH
3)
2CHCH
2180-182 71 H 2-methyl-pi-allyl 200-202 72 H 1-methyl-propargyl 95-97 73 H 2-butynyl 248-250 74 H C2H
5OCOCH
2 174-176
75 H CH
3CH
2CH
2CH
2CH
2131-133 76 H valerylene base 190-192 77 7-CF3H 157-158 and following compound: 78
mp：208-209
79
mp：203-204
The present invention also comprises by a certain 3-(substituted-phenyl)-1,2 that is made up of the compound and the carrier of weeding activity shown in the general formula (I), 3-benzotriazine-4-ketone compound herbicidal composition.
Other embodiments of the present invention are method of controlling weeds, this method comprises the 3-(substituted-phenyl)-1 with compound shown in the general formula of herbicidally effective amount (I) and acceptable carrier composition, 2,3-benzotriazine-4-ketone compound herbicidal composition imposes on the surface of growth medium of the places of described weeds or described weeds or described weeds.
3-of the present invention (substituted-phenyl)-1,2,3-benzotriazine-4-ketone compound 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 John W.McCutcheon, the publication Detergents and Emulsifiers of company, Annual.Allured PublishingCompany, Ridgewood, New Jersey finds among the U.S.A..
3-of the present invention (substituted-phenyl)-1,2,3-benzotriazine-4-ketone compound 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 (substituted-phenyl)-1,2,3-benzotriazine-4-ketone compound herbicidal composition can mix with fertilizer before using mutually.Used said 3-(substituted-phenyl)-1,2 in a class, in the solid fertilizer composition of 3-benzotriazine-4-ketone compound, fertilizer or getting fat component as ammonium sulfate, ammonium nitrate or ammonium phosphate, can have been applied 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-(substituted-phenyl)-1,2, the ratio of 3-benzotriazine-4-ketone compound 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 of composition 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 the pressed powder of porphyrize as affix, inorganic silicate, carbonate and wetting agent, tamanori and or dispersion agent composition mixture.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, can produce additional advantage and effect thus.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 by claim scope of the present invention not.
Synthetic embodiment
Example 1, the preparation of compound 49:
The ice-water bath cooling down, (2.04 restrain with the 2-nitrobenzoyl chloride in 10 minutes, 90%, 5mmol) drips of solution with methylene dichloride (20 milliliters) formation joins 7-fluoro-6-amino-4H-1,4-benzoxazine-3-ketone (1.78 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.Reaction mixture in entry, is filtered and collects the solid that avales, use hexane and washing respectively, obtain 7-fluoro-6-(2-nitro benzoyl)-4H-1 after the drying, 4-benzoxazine-3-ketone (2.9 grams, productive rate 92%), fusing point:＞248 ℃.
The ice-water bath cooling down; (1.5 restrain with zinc powder in 15 minutes; 16mmol) join 7-fluoro-6-(2-nitro benzoyl)-4H-1 in batches; 4-benzoxazine-3-ketone (1.1 grams; 3.4mmol) with (15 milliliters of 2N ammonium chlorides; 27mmol), in the mixture that THF (25 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)-4-H-1,4-benzoxazine-3-ketone (0.7 gram, productive rate 70%), fusing point:＞251-252 ℃.
The ice-water bath cooling down; in 5 minutes with the 3N sodium nitrite solution (0.6 milliliter, 2.6mmol) be added dropwise to 7-fluoro-6-(2-amino benzoyl)-4H-1,4-benzoxazine-3-ketone (0.6 the gram; 2mmol) in the mixture that forms with 2N hydrochloric acid (7 milliliters), stirred 3 hours under the room temperature.Filter and collect the solid that avales, wash with water, obtain 3-[7-fluoro-2H-1 after the drying, 4-benzoxazine-3 (4H)-6-ketone]-1,2,3-phentriazine-4-ketone (0.55 gram, productive rate 90%), fusing point:＞252 ℃.
Example 2, the preparation of compound 62:
Sodium hydride (0.07 gram, 60%, 1.8mmol) join the 3-[7-fluoro-4H-1 under the frozen water cooling, 4-benzoxazine-3 (4H)-ketone-6-]-1,2,3-phentriazine-4-ketone (0.45 gram, 1.5mmol) in the solution that forms with DMF (15 milliliters), stir under the room temperature add after 10 minutes propargyl bromide (0.25 gram, 80%, 1.6mmol). 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 3-[7-fluoro-4-(N-propargyl)-1,4-benzoxazine-3 (4H)-ketone-6-]-1,2,3-phentriazine-4-ketone (0.3 gram, productive rate 60%), fusing point: 246-248 ℃.
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 3.
Table 3: the weeding activity of compound in the part general formula I
[before seedling, after (1200 g/has)/seedling, (1200 g/has)] compound, BYG, FOX, MA, TOM, VEL1, 0/0, 0/0, 0/0, 0/0, 0/402, 0/15, 0/0, 0/0, 0/15, 0/605, 0/0, 0/60, 0/0, 0/0, 0/309, 0/0, 0/20, 0/0, 0/0, 0/014, 0/0, 60/0, 0/0, 0/0, 0/015, 0/0, 75/0, 0/0, 0/0, 0/018, 0/0, 0/0, 0/0, 0/15, 0/9819, 0/10, 0/0, 0/0, 0/50, 0/9022, 0/0, 0/0, 0/0, 0/0, 0/8024, 0/0, 0/0, 0/0, 0/0, 0/7026, 10/98, 98/90, 0/0, 60/95, 15/10027, 20/0, 20/0, 0/0, 10/10, 10/8028, 0/0, 0/0, 0/0, 0/0, 0/8031, 0/0, 0/0, 0/0, 10/0, 10/033, 0/20, 0/0, 0/0, 0/40, 0/10034, 0/0, 0/0, 0/0, 0/80, 0/8035, 0/0, 0/0, 0/0, 0/0, 0/4036, 0/70, 90/50, 0/0, 0/25, 80/10037, 20/99, 100/98, 0/100, 100/100, 85/10038, 0/0, 0/0, 0/0, 0/20, 0/8039, 0/75, 0/90, 0/0, 0/100, 0/10040, 0/60, 0/40, 0/80, 0/85, 0/10042, 0/60, 0/30, 0/0, 0/100, 0/10043, 0/80, 0/85, 0/0, 0/20, 0/10044, 0/80, 0/95, 0/95, 0/80, 0/10046, 0/0, 0/0, 0/0, 0/85, 0/9049, 0/0, 0/0, 0/0, 0/0, 0/2050, 0/0, 0/30, 0/0, 0/85, 0/7051, 95/95, 80/95, 0/80, 85/90, 80/10052, 80/80, 80/80, 20/95, 90/95, 60/9553, 60/85, 100/100, 0/100, 100/100, 100/10054, 80/70, 90/95, 0/80, 100/100, 100/10055, 30/90, 80/90, 20/100, 70/100, 100/10056, 0/60, 20/60,--*,--, 40/10057, 85/60, 30/0, 0/0, 100/90, 100/10058, 20/80, 80/95, 0/85, 90/90, 20/10059**, 60/80, 100/80,--,--, 100/10060, 85/90, 90/95, 0/80, 100/100, 100/10061, 30/90, 85/20, 0/60, 20/80, 100/10062, 95/85, 90/95, 60/100, 90/90, 90/10063, 0/70, 95/60, 0/80, 80/80, 0/10064, 20/90, 70/90, 0/90, 90/95, 0/9565, 20/95, 60/30, 0/0, 60/80, 40/10066, 30/90, 90/95, 0/30, 90/90, 0/10067, 95/95, 85/90, 20/70, 70/100, 100/10068, 95/95, 20/30, 0/0, 20/95, 70/10069, 30/95, 0/90, 0/30, 0/60, 40/10070, 30/85, 80/90, 0/15, 90/95, 20/9571, 20/85, 90/80, 0/90, 100/95, 0/10072, 95/80, 95/95, 20/100, 100/100, 100/10073, 20/80, 90/30, 0/0, 0/40, 0/9574, 0/0, 0/0, 0/0, 0/0, 0/4075, 0/60, 0/0, 0/0, 0/70, 0/7076, 0/0, 0/0, 0/0, 0/0, 0/6078, 0/0, 0/30, 0/0, 0/20, 0/80*: do not survey * *: 600 g/has
Table 3: weeds title
| 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 (8)
1. 3-(substituted-phenyl)-1,2 with weeding activity, the 3-benzotriazine-4-ketone compound is characterized in that the general formula of title compound of the present invention (I) is:
Wherein:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be H, halogen, ethanoyl;
X
2Be H or halogen;
X
3Be halogen, CN, NO
2
X
5Be H or halogen;
X
4Be halogen, (C
1-C
8) alkyl, 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
8) alkyl sulfonyl amino, (C
1-C
8) alkyl sulfonyl (C
1-C
2) alkylamino, (C
1-C
4) carbalkoxy (C1-C2) alkoxyl group;
Work as X
1Be halogen or ethanoyl, X
2And X
5During for hydrogen, X
3And X
4Can form benzo 5-as follows or 6-unit heterocycle:
Wherein:
L is O, S;
R
2Be H or (C
1-C
4) alkyl;
R
3Be H, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (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, cyanogen (C
1-C
6) alkyl, amino or hydroxyl; R
4Be H, fluorine, (C
1-C
3) alkyl; Work as X
1, X
3Be halogen, X
2During for hydrogen, X
4And X
5Can form benzo 5-as follows or 6-unit heterocycle:
Wherein:
Y is O, S or-NR
6
Y ' be Y or-CO;
R
5Be H, halogen, (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, CN, (C
1-C
6) hydroxyalkyl ,-CO
2R
8, aldehyde radical, (C
1-C
8) the alkane carbonyl
Base, (C
1-C
6) alkylthio, (C
1-C
6) alkyl sulphinyl, (C
1-C
6) alkyl sulphonyl, halo (C
1-C
6) alkane
Sulfenyl, halo (C
1-C
6) alkyl sulphonyl, halo (C
1-C
6) alkyl sulphinyl, carboxyl;
R
6, R
8Be respectively H, (C
1-C
6) alkyl, (C
3-C
6) thiazolinyl, (C
3-C
6) alkynyl;
R
7Be H, halogen, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (C
1-C
8) alkyl carbonyl, NO
2
And its esters preparation.
2. compound as claimed in claim 1 is characterized in that:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be H, halogen, ethanoyl;
X
2Be H;
X
3Be halogen, CN, NO
2
X
5Be H;
X
4Be halogen, (C
1-C
8) alkyl, halo (C
1-C
4) alkyl, (C
1-C
4) 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
4) carbalkoxy (C
1-C
2) alkoxyl group;
Work as X
1During for halogen, X
3And X
4Can form benzo 5-as follows or 6-unit heterocycle:
Wherein:
L is O, S;
R
2Be H or (C
1-C
4) alkyl;
R
3Be H, (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (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) alkane
Base, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl, cyanogen (C
1-C
6) alkyl, amino or hydroxyl;
R
4Be H, fluorine, (C
1-C
3) alkyl;
And its esters preparation.
3. compound as claimed in claim 2 is characterized in that:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be halogen;
X
2Be H;
X
3Be halogen, CN, NO
2
X
5Be H;
X
4Be halogen, (C
1-C
8) alkyl, halo (C
1-C
4) alkyl, (C
1-C
4) 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
4) carbalkoxy (C
1-C
2) alkoxyl group;
And its esters preparation.
4. compound as claimed in claim 2, its general formula is as follows:
Wherein:
M is 1 to 4;
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, CN, phenoxy group, or by 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, the phenoxy group that CN replaces;
X
1Be H, halogen;
L is O, S:
R
2Be H or (C
1-C
3) alkyl;
R
3Be (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (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) alkane
Base, (C
3-C
6) alkynes oxygen (C
1-C
2) alkyl, cyanogen (C
1-C
6) alkyl, amino or hydroxyl;
And its esters preparation.
5. compound as claimed in claim 4, its general formula is as follows;
Wherein:
R
3Be (C
1-C
6) alkyl, halo (C
1-C
6) alkyl, (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, cyanogen (C
1-C
6) alkyl, amino or hydroxyl; And its esters preparation.
6. herbicidal composition, it is characterized in that: said composition comprises described compound of claim 1 and acceptable carrier thereof, wherein the weight content of active ingredient is 0.1-99%.
7. described compound of claim 1 and the application of composition in management of weeds thereof.
8. control method for weed for one kind, it is characterized in that: this method comprises the herbicidal composition as claimed in claim 6 of using herbicidally effective amount on growth medium of these weeds or these weeds or place.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001230239A CN1150173C (en) | 2000-09-26 | 2000-09-26 | 3-(substituted phenyl) 1,2,3-benzotriazine-4-ketone compound with weeding activity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001230239A CN1150173C (en) | 2000-09-26 | 2000-09-26 | 3-(substituted phenyl) 1,2,3-benzotriazine-4-ketone compound with weeding activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1345722A true CN1345722A (en) | 2002-04-24 |
| CN1150173C CN1150173C (en) | 2004-05-19 |
Family
ID=4589505
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875569A (en) * | 2012-09-27 | 2013-01-16 | 南开大学 | Isoxazole pyrimidone (or triazone) compounds with herbicidal activity and anti-liver cancer activity |
| CN105017258A (en) * | 2014-12-30 | 2015-11-04 | 南开大学 | Prepartion and application of pyrazolo[3,4-d][1,2,3]triazine-4-one derivative |
| CN112094243A (en) * | 2019-09-03 | 2020-12-18 | 山东先达农化股份有限公司 | Compound containing benzotriazine structure, preparation method and application thereof, and herbicide |
-
2000
- 2000-09-26 CN CNB001230239A patent/CN1150173C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875569A (en) * | 2012-09-27 | 2013-01-16 | 南开大学 | Isoxazole pyrimidone (or triazone) compounds with herbicidal activity and anti-liver cancer activity |
| CN105017258A (en) * | 2014-12-30 | 2015-11-04 | 南开大学 | Prepartion and application of pyrazolo[3,4-d][1,2,3]triazine-4-one derivative |
| CN112094243A (en) * | 2019-09-03 | 2020-12-18 | 山东先达农化股份有限公司 | Compound containing benzotriazine structure, preparation method and application thereof, and herbicide |
| CN112094243B (en) * | 2019-09-03 | 2022-03-01 | 山东先达农化股份有限公司 | Compound containing benzotriazine structure, preparation method and application thereof, and herbicide |
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| Publication number | Publication date |
|---|---|
| CN1150173C (en) | 2004-05-19 |
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