CN88103413A - Pyrylium compound - Google Patents

Pyrylium compound Download PDF

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Publication number
CN88103413A
CN88103413A CN198888103413A CN88103413A CN88103413A CN 88103413 A CN88103413 A CN 88103413A CN 198888103413 A CN198888103413 A CN 198888103413A CN 88103413 A CN88103413 A CN 88103413A CN 88103413 A CN88103413 A CN 88103413A
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alkyl
formula
compound
hydrogen
nitro
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理查德·詹姆斯·安德逊
李诗妇
加利·韦恩·吕阿
卡罗尔·鲁思·斯科特
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Sandoz AG
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
    • C07D211/86—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings

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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Pyrane Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Benzoyl-2H-the pyrans-3 that replaces, 5-(4H, 6H)-two ketone and relevant compound, its intermediate, its synthetic method, and the application of said compound in controlling weeds.

Description

The present invention relates to the benzoyl-2H-pyrans-3 of new replacement, 5-(4H, 6H)-two ketone and allied compound and intermediate thereof, and their the synthetic and application of said compound in controlling weeds.
More particularly, compound of the present invention is a compound shown in the following formula I:
X is an oxygen in the formula, S(O) n or NR 11;
R 1, R 2, R 3, R 4Be respectively hydrogen separately, C 1-8Alkyl or COOR 9, perhaps R 1And R 2Constitute C together 3-6Alkylidene group;
R 5By any C that replaces of 1 to 6 halogen atom 1-8Alkyl; By any C that replaces of 1 to 6 halogen atom 1-8Alkoxyl group; S(O) n ' R 12; Halogen; Or nitro;
R 6And R 7Be respectively hydrogen separately; Halogen; By any C that replaces of 1 to 6 halogen atom 1-8Alkyl; By any alkoxyl group that replaces of 1 to 6 halogen atom; C 1-8Alkyl-carbonyl; C 1-8Alkoxy carbonyl; NR 9R 10; SO 2NR 9R 10; S(O) n ' R 12; Nitro; Or cyano group; Its prerequisite is: R 6And R 7All must not be connected on 6;
R 8Be hydrogen, C 1-8Alkyl, C 1-8Alkyl-carbonyl, C 1-8Alkoxy carbonyl; Benzoyl, C(O) NR 9R 10, C 1-8Alkyl sulphonyl, P(O)-(OR 11) 2Or R 9P(O) OR 11;
R 9And R 10Be respectively hydrogen or C separately 1-8Alkyl;
R 11Be C 1-8Alkyl; With
R 12Be the C that is replaced arbitrarily by 1 to 6 halogen atom 1-8Alkyl; With
N and n ' respectively do for oneself 0,1 or 2.
Prepare 2-benzoyl-1 according to being similar to by corresponding 1-benzoyloxy-1-cycloalkanes alkene-3-ketone compound, the method for 3-cycloalkanes two ketones and ethers thereof and ester class can make the formula I compound.
The formula II compound through reset an accepted way of doing sth (I is compound a), continues it, if necessary, with formula (I is compound etherificate or an esterification accepted way of doing sth (I b) compound a), can obtain the formula I compound thus, and formula II is:
Figure 88103413_IMG4
X and R in the formula 1-R 7As defined above, formula (I a) is:
Figure 88103413_IMG5
R in the formula 8=H and X and R 1-R 7As defined above, formula (I b) is:
Figure 88103413_IMG6
R in the formula 18Be C 1-8Alkyl, C 1-8Alkyl-carbonyl, C 1-8Alkoxy carbonyl, benzoyl, (CO) NR 9R 10, C 1-8Alkyl sulphonyl, P(O)-(OR 11) 2Or R 9P(O) OR 11, and, X and R 1-R 7As defined above.
For example, in the presence of the cyano group negatively charged ion and/or hydrocyanic acid of catalytic amount, and the alkaline moderate alkali of adding molar excess (so that forming enol ester), can carry out above-mentioned rearrangement reaction.The solvent that this reaction is adopted is to be the inert solvent under this reaction conditions, for example, 1,2-ethylene dichloride, toluene, acetonitrile, methylene dichloride, ethyl acetate, dimethyl formamide (DMF) or methyl iso-butyl ketone (MIBK) (MIBK).According to the character of reactant and cyanide source, the temperature of carrying out rearrangement reaction can be up to 80 ℃.In some cases, for example in the time might generating excessive by product, the top temperature of reaction should remain on about 40 ℃.
Preferred cyanide source comprises: alkali metal cyanide, for example sodium cyanide and potassium cyanide; The cyanalcohol that the methyl alkyl ketone of 1-4 carbon atom is arranged on alkyl, for example, the cyanalcohol of acetone or methyl iso-butyl ketone (MIBK); Phenyl aldehyde or C 2-5The cyanalcohol of alkanoic (as: acetaldehyde, propionic aldehyde etc.); Zinc cyanide; Three (low alkyl group) silyl prussiate, particularly trimethylsilyl cyanide; And hydrocyanic acid itself.In cyanalcohol, preferred cyanide source is an acetone cyanohydrin.Press enol ester and calculate, employed cyanide source amount can be up to about 50 moles of %.Preferred cyanide source amount generally is about 1-10 mole %.
Term " alkali that alkalescence is moderate " means the following material that can play the effect of alkali, i.e. intensity or the effect circle alkali between highly basic as oxyhydroxide (can make the enol ester hydrolysis) and the weak base as supercarbonate (can not play effective function).The alkaline moderate alkali that is applicable to this reaction comprises organic bases (as: tertiary amine) and mineral alkali (as: alkaline carbonate and phosphoric acid salt).Suitable tertiary amine comprises trialkylamine, triethylamine for example, three alkanolamines, trolamine for example, pyridine.Suitable mineral alkali comprises salt of wormwood and tertiary sodium phosphate.Make alkali charge be about 1 to 4 moles/mole enol ester, preferably about 1.3-2 moles/mole enol ester.
When cyanide source is an alkali metal cyanide, especially during potassium cyanide, in this reaction, can comprise phase-transfer catalyst.Concrete suitable phase-transfer catalyst is a crown ether.
For example, (I is compound and a) formula III compound reaction a), perhaps in the presence of the moderate alkali of alkalescence, by the reaction of formula (I is compound and b a)) formula IV compound, can make formula (I b) compound, and formula III is: R ' by formula under catalyzer 8The OH(III), R ' in the formula 8As defined above, formula IV is: R ' 8Q, R ' in the formula 8As defined above, Q is a halogen.
Above-mentioned and the reaction formula III compound can be carried out in the presence of vitriol oil and so on catalyzer.In the solvent (as: methyl alcohol) that itself also is reactant, and at elevated temperatures, help reaction and carry out.
Above-mentioned and the reaction formula IV compound is in the presence of the moderate alkali of alkalescence (as: triethylamine or pyridine), is preferably in room temperature (RT) or is lower than under the room temperature and carry out.
According to the known method operation, can from the reaction mixture that forms the formula I compound, reclaim the formula I compound.
Starting raw material that uses in methods described herein and reagent both can be known, also can be unknown so far compounds, and the latter can be by being similar to methods described herein or currently known methods makes.
Because tautomerism, formula (I a) compound can have following four kinds of structural formulas:
Figure 88103413_IMG7
In the embodiment of this invention, X is oxygen preferably, sulphur or NR 11
If substituent R 1-R 7And R 9-R 12In any substituting group be that or when comprising halogen, these halogens preferably are selected from bromine, chlorine and fluorine.
If R 1-R 7And R 9-R 12In arbitrary substituting group be or to comprise C 1-8Alkyl, it is the alkyl of 1 to 4 carbon preferably.
If R 5-R 8In arbitrary substituting group be or to comprise C 1-8Alkoxyl group, it is the alkoxyl group of 1 to 4 carbon atom preferably.
R 5Generally mean the C that replaces arbitrarily by halogen 1-4Alkyl, C 1-4The n ' of alkyl-S(O), halogen or nitro; But better be methyl, CF 3, C 1-3Alkyl sulphonyl, chlorine, bromine or nitro, preferably nitro, methyl or methylsulfonyl.
R 6Generally mean hydrogen, by any C that replaces of halogen 1-4Alkyl, C 1-4The n ' of alkyl-S(O), the C that replaces arbitrarily by halogen 1-4The n ' of alkyl-S(O), the C that replaces arbitrarily by halogen 1-4Alkoxyl group; Halogen, or nitro; But hydrogen preferably, CF 3, C 1-3Alkyl sulphonyl, chloro C 1-3Alkyl sulphonyl, methoxyl group, chlorine, fluorine or nitro.
R 6Better be in the 4-position, preferably the person is 4-Cl.
R 7Hydrogen preferably.
R 8Better be C 1-8Alkyl, C 1-8Alkyl-carbonyl, benzoyl, C 1-8Alkoxy carbonyl or C 1-8Alkyl sulphonyl; Preferably be selected from C 1-8Alkyl-carbonyl and benzoyl become ester group.
Preferred R 8Examples of groups has: hydrogen, C 1-4Alkyl, C 1-4Alkyl-carbonyl, benzoyl or C 1-4Alkyl sulphonyl.
The same clan of preferred formula I compound should have one or more following features:
At least R 1, R 2, R 3, R 4One of be COOR 9, better be COOH or C 1-4Alkoxy carbonyl is preferably C 1-4Alkoxy carbonyl.
R 1, R 2, R 3, R 4In have at least 3 not to be hydrogen.
R 1, R 2, R 3Be C 1-4Alkyl, R 1, R 2, R 3, R 4Be C 1-4The alkyl person is better.
Employing is emerged preceding or the aftertreatment of emerging, and new formula I compound can be used for controlling weeds.Also can be with them as plant-growth regulator.These compounds can be used by following formulation: dust agent, granule, solution, emulsion, moist powder, fluid and suspension agent.According to conventional process, The compounds of this invention can be applied to weeds or its growth region, its herbicidally effective amount generally is about half pound every acre or still less, is at most ten pounds.Use The compounds of this invention in weeds " growth region ", comprise it is applied to seed, plant (weeds) or plant materials, or soil.
" weedicide " used herein speech means the active ingredient that tool improve to be handled the plant-growth performance, and these active ingredients can make plant receive because of poisoning or plant growth regulation to delay plant-growth or damage plant effectively so that with its effect of killing.
When conduct was emerged preceding or emerged back herbicide application The compounds of this invention, the result shows: they were to wide leaf grass, and grass and sedge have herbicide effect efficiently.
With regard to controlling weeds is used the formula I compound, as herbicidal composition, can be with the formula I compound, or its mixture is with being applicable to that the acceptable diluent that weeds or its growth region are used uses.These compositions also are parts of the present invention.They can obtain with well-known method.
For the ordinary skill in the art, be easy to determine the best using method of The compounds of this invention by routine test (as: greenhouse experiment, small area test).
Suitable prescription contains 0.01-99%(weight) active ingredient, 0-20% tensio-active agent, the solid of 1-99.99% or liquid diluent.For active ingredient, a high proportion of tensio-active agent is useful sometimes, it can be added in the prescription or by container to mix promptly.In the dispenser formulation of composition, the content of active ingredient is generally in 0.01-25%(weight) between.Certainly, the concentration of active ingredient just can be depending on application target, the physical properties of compound, and application process.The content that concentrates active ingredient in the formulation with preceding dilute compositions generally between 2% and 90%, be preferably in 5% and 80%(weight) between.
Effective prescription of formula I compound comprises dust agent, granule, and suspension concentrate, moist powder, fluid, or the like.They can be made by conventional process, for example, the formula I compound are mixed promptly with thinner and any other composition.
In addition, also can use the formula I compound by encapsulated form.
The formula I compound can share with cyclodextrin, makes to be applicable to insect or its breeding ground the cyclodextrin of using parcel mixture.
The acceptable additive can improve the effect of active ingredient on the use agricultural in this herbicidal composition, and reduces foaming, caking, corrosion.
This paper said " tensio-active agent " is meant acceptable material on the agricultural with following character, promptly promotes emulsification, sprays, and is moistening, disperses or have other to improve surperficial effect.The example of tensio-active agent has: sodium lignosulfonate, Sulfuric acid,monododecyl ester, sodium salt.
The agricultural that is meant this paper said " thinner " go up acceptable be used for condensed matter is diluted to can use or the liquid or solid material of institute's phase concentration.For example, for dust agent or granule, can be talcum powder, kaolin or diatomite; For liquid concentrates, can be alkane, as: dimethylbenzene-or alcohol, as: Virahol for the liquid application agent, can be water or diesel oil.
Composition of the present invention also can contain the compound of other biologically actives, and for example, be used for preventing and treating the compound of the similar or subsidy herbicide effect of having of wide range grass or have detoxifcation, fungicidal, desinsection, or lure the compound of worm effect.
The following example is explained to enforcement of the present invention.Temperature is a centigradetemperature.RT is a room temperature, and umber and per-cent are all calculated by weight.
Embodiment 1
2,2-dimethyl-4-(4-chloro-2-nitro benzoyl)-2H-thiapyran-3,5-(4H, 6H) diketone
To be mixed with 2,2-dimethyl-5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-thiapyran-3-ketone (8.3g, 24.3mmol), triethylamine (6.8ml, 48.7mmol) and the 35ml acetonitrile of acetone cyanohydrin (0.5ml) under room temperature, stirred 16 hours.This reaction mixture is concentrated, and be dissolved in the ether.With rare HCl and salt water washing ether extracted liquid, drying also is evaporated to dried.With thick purifying products, obtain 2,2-dimethyl-4-(4-chloro-2-nitro benzoyl)-2H-thiapyran-3,5-(4H, 6H)-diketone (compound 1. Table As).
Embodiment 2
2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-2H-pyrans-3,5-(4H, 6H)-diketone
Cyanalcohol (0.5ml) is added to is mixed with 2,2,6,6-tetramethyl--5-(4-chloro-2-nitrobenzoyl acyloxy)-3, and 6-dihydro-2H-pyrans-3-ketone (5.97g, 16.9mmol) and triethylamine (4.70ml, 33.8mmol) the 30ml acetonitrile in, and this mixture stirred under room temperature 24 hours.Dilute this reaction mixture with ether, and with 5% K 2CO 3Extraction with aqueous solution it.With concentrated hydrochloric acid acidifying water layer, and with ether extraction it.Merge organic layer, and drying, evaporation obtains light yellow crystal, and the latter is purified, obtains 2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-2H-pyrans-3,5-(4H, 6H)-diketone (compound 8, Table A).
Embodiment 3
N-methyl-4-(2,4-dichloro-benzoyl base) piperidines-3, the 5-diketone
With acetone cyanohydrin (0.05g, 0.06ml, 0.67mmol) be added in the 30ml acetonitrile and be mixed with 5-(2,4-dichloro-benzoyl oxygen base)-the 1-methyl isophthalic acid, the 6-dihydro-3-(2H)-pyridone (2.0g, 6.7mmol) and triethylamine (1.35g, 1.9ml is in mixture 13.3mmol).After nearly 30 minutes, remove acetonitrile, use the methylene dichloride diluted reaction mixture, with dilute hydrochloric acid and salt water washing, drying, be evaporated to dried, purified after, obtain N-methyl-4-(2,4-dichloro-benzoyl base)-piperidines-3,5-diketone (compound 22, Table A).
Embodiment 4
According to embodiment 1,2, or 3 method, by corresponding benzoyl enol ester, triethylamine and acetone cyanohydrin have made each compound of listing in the Table A.
Embodiment 5
2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-methoxyl group-3,6-dihydro-2H-pyrans-3-ketone
To contain 2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-2H-pyrans-3,5-(4H, 6H)-(0.90 gram, 2.54mmol) the 20ml methanol solution with two vitriol oils heated 48 hours under refluxing diketone.Reaction mixture is concentrated, and use the ether extraction residue.With sodium bicarbonate aqueous solution and salt water washing ether extracted liquid, dry and be evaporated to driedly, obtain 2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-methoxyl group-3,6-dihydro-2H-pyrans-3-ketone (compound 65).
Embodiment 6
2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-acetoxy-3,6-dihydro-2H-pyrans-3-ketone
In 0 ℃; with the Acetyl Chloride 98Min. (0.27g that mixes in the 5ml methylene dichloride; 3.39mmol) drips of solution is added to and contains triethylamine (0.47ml; 3.39mmol) methylene dichloride (10ml) in 2,2,6; 6-tetramethyl--4-(4-chloro-2-nitro benzoyl) 2H-pyrans-3; 5-(4H, 6H)-(0.80g is in mixture 2.26mmol) for diketone.The gained mixture was stirred 30 minutes, then with the methylene dichloride dilution, washing, drying is evaporated to driedly, obtains 2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-the 5-acetoxy-3,6-dihydro-2H-pyrans-3-ketone (compound 66).
Embodiment 7
According to embodiment 6 described methods,, 6-tetramethyl--4-(4-chloro-2-nitro benzoyl) by 2,2,6-and 2H-pyrans-3,5-(4H 6H)-diketone and corresponding acyl chloride reaction, has made the final compound on I hurdle.
Ⅰ
67.2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-propionyloxy-3,6-dihydro-2H-pyrans-3-ketone, (oily matter).
68.2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-isobutyl acyloxy-3,6-dihydro-2H-pyrans-3-ketone (oily matter).
69.2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-new pentane acyloxy-3,6-dihydro-2H-pyrans-3-ketone; M.p.79 °.
70.2,2,6,6-tetramethyl--4-(4-chloro-2-nitro benzoyl)-5-benzoyloxy-3,6-dihydro-2H-pyrans-3-ketone, m.p.109 °.
Embodiment 8
2,6-dimethyl-2-ethoxycarbonyl-4-(4-chloro-2-nitro benzoyl)-2H-pyrans-3, the 5-diketone
Will be by 2,6-dimethyl-2-ethoxycarbonyl-5-(4-chloro-2-nitrobenzoyl acyloxy)-3, and 6-dihydro-2H-pyrans-3-ketone (3.5g, 8.8mmol), triethylamine (2.5ml, 17.6mmol) and the mixture formed of acetone cyanohydrin (0.5ml) under room temperature, stir and spend the night.This reaction mixture is concentrated, residue is dissolved in the ether, and extracts it.Merge organic extracting solution, with dilute hydrochloric acid and salt water washing, drying, evaporation.Crude product obtains 2 through chromatography purification, 6-dimethyl-2-ethoxycarbonyl-4-(4-chloro-2-nitro benzoyl)-2H-pyrans-3, the 5-diketone.
Embodiment 9
A. suspension concentrate 20% 50%
Compound 8 20.00 50.00
Distilled water 63.83 34.71
Propylene glycol 8.55 6.55
Naphthalene formal sodium sulfate 6.82 7.82
Collodial silica magnalium 0.50 0.25
Xanthan gum 0.27 0.14
Be blended in the alkyne diol (SURFYNOL in the propylene glycol RTG5) 0.03 0.03
Said mixture is mixed the particle that also wet-milling becomes the 5-10 micron.
B. wet-milling-50%
Compound 15 50.00
Naphthalene formal sodium sulfate 5.00
Kaolin 5.00
Precipitated silica (amorphous) 5.00
Cationic additive (MORWET REFW) 2.00
Above-mentioned composition is mixed, wet-milling, and the gained mixture is added to the water that is used for spraying.
Table A
Figure 88103413_IMG8
Fusing point
Compounds X R 1R 2R 3R 4R 5R 6R 7(℃)
1 S H H CH 3CH 3NO 24-Cl H oil
2 S H H H CH 3NO 24-Cl H 98
3 S H CH 3CH 3CH 3NO 24-Cl H 52
4 S CH 3CH 3CH 3CH 3NO 24-Cl H 52
5 O H H H CH 3NO 24-Cl H 86
6 O H H CH 3CH 3NO 24-Cl H 104
7 O H CH 3CH 3CH 3NO 24-Cl H oil
8 O CH 3CH 3CH 3CH 3NO 24-Cl H 87
9 O CH 3CH 2CH 3CH 3CH 2CH 3NO 24-Cl H 67
10 O CH 3CH 3CH 3CH 3Cl 4-Cl H oil
11 O CH 3CH 3CH 3CH 3Cl 4-Br H
12 O CH 3CH 3CH 3CH 3Cl 4-NO 2H 128
13 O CH 3CH 3CH 3CH 3Cl 4-SO 2CH 3H 140
14 O CH 3CH 3CH 3CH 3NO 24-CF 3H
15 O CH 3H CH 3H NO 24-Cl H 121
16 O H H H H NO 24-Cl H 164
17 O CH 3CH 3CH 3CH 3NO 2H H 128
18 O CH 3CH 3CH 3CH 3SO 2CH 34-Cl H
19 S H CH 3CH 3CH 3Cl 4-Cl H 100
20 S CH 3CH 3CH 3CH 3Cl 4-Cl H 67.5
21 S CH 3CH 3CH 3CH 3Cl 4-Br H 81.5
22 NCH 3H H H H Cl 4-Cl H
Table A (continuing)
Fusing point
Compounds X R 1R 2R 3R 4R 5R 6R 7(℃)
23 O CH 3CH 2CH 3CH 3CH 3NO 24-Cl H 82
24 O CH 3CH 3CH 3CH 3NO 24-Br H 90
25 O CH 3CH 3CH 3CH 3NO 24-F H 95
26 O CH 3CH 3CH 3CH 3CF 3H H oil
27 O CH 3CH 3CH 3CH 3Cl 4-F H 70
28 O CH 3CH 3CH 3CH 3F 4-Cl H 223
29 O CH 3CH 3CH 3CH 3NO 23-Cl H 130
30 O CH 3CH 3CH 3CH 3NO 23-CH 3H 162
31 O H CH 2CH 3H H NO 24-Cl H oil
32 O H CH 2CH 3H CH 3NO 24-Cl H 97
33 O H CH 2CH 3H CH 3NO 24-Br H 111
34 O CH 3CH 2CH 3H H NO 24-Cl H 102
35 O CH 3CH 2CH 3H CH 3NO 24-Cl H oil
36 O CH 3H H CH 2CH 3NO 24-F H 61
37 O CH 3CH 3H H NO 24-F H oil
38 O CH 3CH 3CH 3CH 3NO 24-SO 2CH 3H 151
39 O CH 3CH 3H H NO 24-SO 2CH 3H oil
40 O H CH 3H CH 3NO 24-SO 2CH 3H 140-143
41 O H CH 2CH 3H CH 3NO 24-SO 2CH 3H oil
42 O H CH 2CH 3H CH 3Cl 4-SO 2CH 3H oil
43 O H H CH 3CH 3Cl 4-SO 2CH 3H oil
44 O CH 3CH 3CH 3CH 3Cl 4-SO 2CH 33-Cl 64.5
45 O H CH 3H CH 3Cl 4-Cl 3-Cl oil
46 O H CH 2CH 2CH 3H CH 3NO 24-Cl H oil
47 O-CH 2-CH 2-CH 2-CH 2-H H NO 24-Cl H oil
Table A (continuing)
Fusing point
Compounds X R 1R 2R 3R 4R 5R 6R 7(℃)
48 O H CH 2CH 3CH 3CH 3NO 24-Cl H oil
49 O H CH 2CH 3H CH 2CH 3NO 24-Cl H 83
50 O H CH 3H CH 2CH 3NO 24-H H 105
51 O CH 3CH 3CH 3CH 3NO 24-CH 3H 93
52 O CH 3CH 3CH 3CH 3CH 34-Br H oil
53 O CH 3CH 3CH 3CH 3CF 34-F H oil
54 O CH 3H CH 2CH 3H NO 24-F H oil
55 O CH 3H CH 2CH 3H NO 24-SCH 3H 103
56 O CH 3H CH 2CH 3H NO 24-SCH 2CH 3H oil
57 O CH 3H CH 2CH 3H Cl 4-SCH 2CH 3H oil
58 O CH 3H CH 3H Cl 4-SCH 2CH 3H oil
59 O CH 3CH 3CH 3CH 3NO 24-SCH 2CH 3H 48.5
60 O CH 3CH 3CH 3CH 3NO 24-SCH 3H 97.5
61 S CH 3CH 3CH 3CH 3CF 3H H oil
62 S H H H H NO 24-Cl H 172
63 NCH 3H H H CH 3NO 24-Cl H 285
64 NCH（CH 3） 2H CH 3H CH 3NO 24-Cl H 190
71 O H CH(CH 3) 2H CH 3NO 24-Cl H oil
72 O CH 3CH 3CH 3CH 3Cl 4-Cl 3-Cl 78
73 O CH 3CH 3CH 3CH 3Cl 4-SO 2CH 3H oil
74 O H CH 3H CH 2CH 3CF 34-F H 61
Biological activity
Embodiment 10
Measured the preceding weeding activity of emerging of preferred compound of the present invention as follows: the sowing weed seed, and use by water (17%) the solution impregnation soil that tensio-active agent (0.17%) and a certain proportion of test-compound (1kg/ hectare) are formed.Two weeks were made mark after treatment.Handle the tender foxtail of grass (GR), pasture and water, shattercane, wild avena sativa, wide leaf grass (BL) year living morning glory, mustard, nightshade, piemarker.The previous crops of emerging of compound is with listing among the following table B.
Embodiment 11
Measured weeding activity after the emerging of The compounds of this invention by following method: use by water/acetone (1: 1) seedlings of cereal crops of tensio-active agent (0.5%) and the selected weeds of spray solution formed according to the test-compound of the ratio of 1kg/ hectare.Two weeks were made record after spraying, and handled the tender foxtail of grass (GR), pasture and water, shattercane, wild avena sativa, wide leaf (GR) year living morning glory, mustard, soybean, piemarker.Table B has listed the back effect of on average emerging of these compounds below.
Table B
% weeding activity (1kg/ hectare)
After emerging before emerging
Compound GR BL GR BL
7 100 100 98 90
8 100 95 100 100
10 100 100 95 82
15 97 98 97 100
17 100 87 100 97
23 100 87 97 100
24 100 97 100 97
25 100 100 100 100
26 56 42 95 81
27 92 95 95 82
32 98 100 78 93
33 100 100 96 100
38 78 78 100 100
40 89 100 55 100
41 97 100 67 100
42 82 97 87 100
44 100 100 100 100
45 95 100 95 100
48 100 100 98 97
49 98 97 98 100
50 100 100 97 100
51 60 100 78 100
52 100 100 100 100
53 88 75 97 100
54 100 100 100 100
55 100 100 100 100
60 100 100 100 100
68 100 100 100 100
69 100 100 100 100
70 100 100 100 100
71 100 100 95 100
72 100 100 72 87
73 73 76 100 100
74 73 67 93 90
Formula II initial compounds as herein described is a known compound, perhaps is new compound in some cases, and the latter can be by making with the similar method of currently known methods or by methods described herein.
Therefore, in the presence of the moderate alkali of alkalescence (as: triethylamine), the heterocycle hexane-3 of general formula V, 5-diketone (R in the formula 1-R 4As defined above) (Q is a halogen atom in the formula, R with the benzoyl halogen of formula VI 5-R 7As defined above) reaction can make the formula II enol ester.
Figure 88103413_IMG9
By following a) or b) but method synthesis type (V) 2H-pyrans-3,5-(4H, 6H)-diketone (X is an oxygen in the formula):
A) " people such as Morgan., JACS 79:422(1957) " described method,
B) handle 2 with the diazo acetic acid N2 alkyl ester, the furanidine-3 that 5-replaces, the 4-diketone (people such as Korobitsyna., J.Gen.Cheml USSR 27:1859(1957)), in the presence of water, heat then.
By sodium methylate and formula (VII) sulfide or sarcosinate (alk=methyl or ethyl, X 1=S or NR 11) reaction, can Synthetic 2 H-thiapyran-3,5-(4H, 6H)-and diketone and formula (V) piperidines-3, the 5-diketone.
Figure 88103413_IMG10
The method for preparing midbody compound that the following example explanation is representative.
Embodiment 12
2,2,6,6-tetramethyl--2H-pyrans-3,5-(4H, 6H)-diketone
With boron-trifluoride etherate (4.8ml, 39.0mmol) be added to mix in the 20ml anhydrous ether 2,2,5,5-4-methyl furan alkane-3, (15.0g is 78.0mmol) in the solution for the 4-diketone.(12.3ml, 117.0mmol), its feed rate should be controlled at not make and put nitrogen and become fierce to add the ethyl diazoacetate mix in the 20ml ether.This mixture in stirring at room 12 hours, is added water then and makes it all standing.This mixture is diluted with ether, and use the salt water washing, use 5%K then 2CO 3Extract.Wash this K with ether 2CO 3Solution, and neutralize with concentrated hydrochloric acid.Extract product with ether, drying, evaporation obtains pink oily 4-ethoxycarbonyl-2,2,6,6-tetramethyl--2H-pyrans-3,5-(4H, 6H)-diketone.
With above-mentioned triketone (5.11g 21.1mmol) is dissolved in the 25ml methyl-sulphoxide, add entry (0.8ml, 42.2mmol).With this mixture in 120 ℃ of heating 1 hour, or till no longer including gas and emitting.Dilute this reaction mixture with ether,, remove and desolvate, grind thick product, obtain white crystals shape 2,2,6 with ether/hexane with saturated NaCl solution washing, 6-tetramethyl--2H-pyrans-3,5-(4H, 6H)-diketone.
Embodiment 13
2,2,6,6-tetramethyl--5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-pyrans-3-ketone
Will be in the 30ml methylene dichloride 2,2,6,6-tetramethyl--2H-pyrans-3,5-(4H, 6H)-(3.59g is 21.1mmol) with 4-chloro-2-nitrobenzoyl chloride (4.63g for diketone, 21.1mmol) mixture be chilled to 0 ℃, drip then triethylamine (2.94ml, 27.4mmol).This mixture in stirring at room 1 hour, is dissolved in the methylene dichloride then, water and salt water washing, steaming desolventizes, and obtains crystalloid 2,2,6,6-tetramethyl--5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-pyrans-3-ketone.
Embodiment 14
2,2-dimethyl-2H-thiapyran-3,5-(4H, 6H)-diketone
Sodium Metal 99.5 (2.03g) is dissolved in the methyl alcohol (25ml), steams then and remove methyl alcohol, obtain sodium methylate, under reduced pressure be dried, be suspended in then in the 50ml benzene.(17.89g 87.6mmol) is added drop-wise in the above-mentioned suspension, stirs 2 hours under room temperature then with acetonyl mercaptoisobutyric acid ethyl ester.With this reaction mixture of water extraction, the benzene layer that inclines washs water layer with ether, extracts with the concentrated hydrochloric acid neutralization and with ether.The combined ether extracting solution, drying is evaporated to driedly, purifiedly obtains 2,2-dimethyl-2H-thiapyran-3,5-(4H, 6H)-diketone.
Embodiment 15
2,2-dimethyl-5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-thiapyran-3-ketone
According to the described method of embodiment, by 2,2-dimethyl-2H-thiapyran-3,5-(4H, 6H)-(4.0g is 25.3mmol) with 4-chloro-2-nitrobenzoyl chloride (5.56g for diketone, 25.3mmol) reaction, obtain little brown oily 2,2-dimethyl-5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-thiapyran-3-ketone.
Embodiment 16
1-methyl-piperidines-3,5-diketone sodium salt
Will by embodiment 14 described by sodium Metal 99.5 (0.87g, 38.0mmol) and the sodium methylate that makes of methyl alcohol (10ml) be suspended in the 30ml benzene, the limit drip N-acetonyl sarkosine methyl esters (6.0g, 38.0mmol), the limit cooling.This mixture was stirred 1.5 hours, and that continues removes benzene, obtains 1-methyl-piperidines-3,5-diketone sodium salt.
Embodiment 17
5-(2,4-dichloro-benzoyl oxygen base)-the 1-methyl isophthalic acid, the 6-dihydro-3-(2H)-pyridone
1-methyl-the piperidines-3 that will get by embodiment 16,5-diketone sodium salt is suspended in 25ml 1, in the 2-ethylene dichloride, and cooling.Dropping mixes 2,4 dichlorobenzyl chloride in the 5ml ethylene dichloride, and (8.0g, 5.3ml 38.0mmol), and stirred this mixture 2 hours under room temperature.Remove and to desolvate, residue is dissolved in the methylene dichloride, water and salt water washing, drying is evaporated to driedly, obtains 5-(2,4-dichloro-benzoyl oxygen base after purified)-the 1-methyl isophthalic acid, the 6-dihydro-3-(2H)-pyridone.
Embodiment 18
2,6-dimethyl-2-ethoxycarbonyl-2H-pyrans-3,5-diketone
Red precipitate (0.5g) is added in 50% the sulphuric acid soln (2ml), with this mixture heating up to 80 ℃, till can seeing white Mercury bisulfate.Add entry (5ml) and ethanol (20ml), and this mixture heating up is extremely refluxed.With 2-(2-(3-fourth alkynyloxy group))-(30.0g 124.0mmol) is added drop-wise in the said mixture that is refluxing 2-methyl-maleic acid diethyl ester, and this mixture stirring is spent the night.Under decompression, remove ethanol then, and residue is dissolved in the ether, use the salt water washing then, drying, evaporation.Behind the thick product of chromatography purification, obtain 2-(2-(3-oxo butoxy))-2-methyl-maleic acid diethyl ester.
With 2-(2-(3-oxo butoxy))-2-methyl-maleic acid diethyl ester (20.0g, 76.8mmol) be added drop-wise to sodium methylate (by the 1.77g(76.8mmol) sodium Metal 99.5 and the 25ml methyl alcohol that mix in 50ml benzene and make) in the suspension, and this mixture stirred spend the night.With this reaction mixture of water extraction, wash water layer with ether, with the concentrated hydrochloric acid neutralization, and extract with ether again, with the extracting solution drying, evaporation obtains 2,6-dimethyl-2-ethoxycarbonyl-2H-pyrans-3,5-diketone
Embodiment 19
2,6-dimethyl-2-ethoxycarbonyl-5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-pyrans-3-ketone
With mix in the 50ml methylene dichloride 2,6-dimethyl-2-ethoxycarbonyl-2H-pyrans-3, the 5-diketone (2.0g, 9.3mmol) and the mixture of 4-chloro-2-nitrobenzoyl chloride be cooled to 0 ℃, the dropping triethylamine that continues (1.69ml, 12.1mmol).Under room temperature, this mixture was stirred 1 hour, then with methylene dichloride dilution, water or salt water washing.With thick product drying, evaporation obtains 2,6-dimethyl-2-ethoxycarbonyl-5-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-pyrans-3-ketone and 2,6-dimethyl-2-ethoxycarbonyl-3-(4-chloro-2-nitrobenzoyl acyloxy)-3,6-dihydro-2H-pyrans-5-ketone.

Claims (15)

1, the method for the following formula I compound of preparation, formula I is:
Figure 88103413_IMG1
In the formula, X is an oxygen, S (O) n or NR ",
R 1, R 2, R 3, R 4Be respectively hydrogen separately, C 1-8Alkyl or COOR 9, perhaps R 1And R 2Constitute C together 3-6Alkylidene group, R 5By any C that replaces of 1-6 halogen atom 1-8Alkyl is by any C that replaces of 1-6 halogen atom 1-8Alkoxyl group, S (O) n ' R 12, halogen, or nitro,
R 6And R 7Be respectively hydrogen separately, halogen is by any C that replaces of 1 to 6 halogen atom 1-8Alkyl is by the alkoxyl group that 1 to 6 halogen atom replaces arbitrarily, C 1-8Alkyl-carbonyl, C 1-8Alkoxy carbonyl, NR 9R 10, SO 2NR 9R 10, S (O) n ' R 12, nitro or cyano group,
Its prerequisite is R 6And R 7All must not be connected on 6,
R 8Be hydrogen, C 1-8Alkyl, C 1-8Alkyl-carbonyl, C 1-8Alkoxy carbonyl, benzoyl, C (O) NR 9R 10, C 1-8Alkyl sulphonyl, P (O)-(OR 11) 2Or R 9P (O) OR 11,
R 9And R 10Be respectively hydrogen or C separately 1-8Alkyl,
R 11Be C 1-8Alkyl and
R 12By any C that replaces of 1-6 halogen atom 1-8Alkyl,
And n and n ' respectively do for oneself 0,1 or 2,
This method comprises X and R in the formula 1To R 7Reset X and R in the accepted way of doing sth as the formula II compound defined in claim 1 1To R 7As the formula defined in claim 1 (I is compound a), continue as required with this formula (I a) compound etherificate or an esterification accepted way of doing sth (I is compound a), and formula II is:
Figure 88103413_IMG2
R in the formula 18Be C 1-8Alkyl, C 1-8Alkyl-carbonyl, C 1-8Alkoxy carbonyl, benzoyl, C (O) NR 9R 10, C 1-8Alkyl sulphonyl, P (O)-(OR 11) 2Or R 9P (O) OR 11
2, the process of claim 1 wherein that X is O or S and R 8Be C 1-8Alkyl, C 1-8Alkyl-carbonyl, benzoyl, C 1-8Alkoxy carbonyl or C 1-8Alkyl sulphonyl.
3, the process of claim 1 wherein that X is NR 11And R 8Be C 1-8Alkyl, C 1-8Alkyl-carbonyl, benzoyl, C 1-8Alkoxy carbonyl or C 1-8Alkyl sulphonyl.
4, the method for claim 1 to 3, wherein R 1, R 2, R 3, R 4In have at least one to be COOR 9
5, the method for claim 1 to 4, wherein, R 1, R 2, R 3And R 4In have at least 3 not to be hydrogen.
6, each method in the claim 1 to 5, wherein R 7Be hydrogen.
7, each method in the claim 1 to 6, wherein R 5By any C that replaces of 1 to 3 halogen atom 1-4Alkyl, C 1-4The n ' of alkyl-S(O), halogen or nitro, R 6Be hydrogen, by any C that replaces of 1 to 3 halogen atom 1-4Alkyl, C 1-4The n ' of alkyl-S(O), halo C 1-4The n ' of alkyl-S(O), the C that is replaced arbitrarily by 1 to 3 halogen atom 1-4Alkoxyl group, halogen or nitro, and be to be in the 4-position.
8, the described method of claim 7, wherein R 5It is nitro.
9, the process of claim 1 wherein R 1, R 2, R 3And R 4Be methyl, X is an oxygen, R 8Be hydrogen, and
A) R 5Be nitro, R 6Be 4-chlorine, R 7Be hydrogen
B) R 5Be methyl, R 6Be the 4-bromine, R 7Be hydrogen
C) R 5Be chlorine, R 6Be the 4-methyl sulphonyl, R 7Be 3-chlorine.
10, herbicidal composition comprises that a certain compound and the agricultural by arbitrary claim limited in the claim 1 to 9 goes up the acceptable thinner.
11, herbicidal composition comprises that a certain compound and the agricultural of producing by the method that arbitrary claim limited in the claim 1 to 9 go up the acceptable thinner.
12, a kind of method of controlling weeds, this method comprise uses herbicidally effective amount, the formula I compound that arbitrary claim limited in the claim 1 to 9 to weeds or its growth region.
13, a kind of method of controlling weeds, this method comprise uses herbicidally effective amount to weeds or its growth region, the formula I compound of producing by each described method in the claim 1 to 9.
14, by each method in the claim 1 to 9, be method herein described in the embodiment basically.
CN198888103413A 1987-06-05 1988-06-04 Pyrylium compound Pending CN88103413A (en)

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