CN87106999A - 2-(2-substituted benzoyl)-4-(replacement)-1, the 3-cyclohexanedione - Google Patents

Abstract

Following formula: compound and salt thereof, wherein R is a halogen, C ₁-C ₂Alkyl or alkoxyl group, trifluoro or difluoro-methoxy, nitro, cyano group, C ₁-C ₂Haloalkyl, RaSO _n-, three or difluoromethyl; R ¹Be hydrogen, C ₁-C ₄Alkyl, halogen, benzene or substituted-phenyl; R ²Be hydrogen or C ₁-C ₄Alkyl or R ¹And R ²Be all C ₂-C ₅Alkylidene group; R ³Be hydrogen, C ₁-C ₄Alkyl, benzene or substituted-phenyl; R ⁴Be hydrogen or C ₁-C ₄Alkyl; R ⁵Be hydrogen, halogen or C ₁-C ₄Alkyl; R ⁶Be halogen, cyano group, nitro, trifluoromethyl ,-C (O)-ORf or-C (O) NR ₂B; R ⁷And R ⁸For: hydrogen, halogen, C ₁-C ₄Alkyl or alkoxyl group, trifluoromethoxy etc.

Description

The application is the part continuation application of the application serial no submitted on October 16th, 1,986 919,277 applications, and later this application is that the application serial no of submitting on August 20th, 1987 is the part continuation application of 086,266 application.

European patent application 135,191,186,118,186,119 and 186,120 have related to some the deweeding compound with following structural formula:

In this structural formula: R-R ⁵, R ⁷And R ⁸Be defined as follows R ^aBe C ₁-C ₄Alkyl.

The present invention relates to the 2-(2-substituted benzoyl)-4-(replaces)-1,3-cyclohexane diketone and as herbicidal purposes.

One of content of the present invention is a kind of Herbicidal combinations, and said composition comprises a kind of activity of herbicide compound 2-(2-substituted benzoyl)-the 4-(replacement)-1,3-cyclohexanedione and relevant inert support.1,5,6 and 4 substituting groups that preferably defined below of 3-cyclohexanedione part replace, and the substituted radical that override is selected for use is fontanel element or methyl.The benzoyl part can be substituted, and is preferably following radicals and replaces.

Another content that is included in the scope of the present invention is the compounds that a class has following structural formula:

In this structural formula:

R is the fontanel element, preferred chlorine or bromine; C ₁-C ₂Alkyl, preferable methyl; C ₁-C ₂Alkoxyl group, preferred methoxyl group; Trifluoromethoxy; Difluoro-methoxy; Nitro; Cyano group; C ₁-C ₂The fontanel substituted alkyl, preferred trifluoromethyl; R ^aSOn-(n is 0 or 2, and is preferred 2, R ^aBe C ₁-C ₂Alkyl, preferable methyl, trifluoromethyl or difluoromethyl), R preferentially selects chlorine, bromine, C for use ₁-C ₂Alkyl, C ₁-C ₂Alkoxyl group, trifluoromethyl, cyano group, nitro, C ₁-C ₂Alkylthio or C ₁-C ₂Alkyl sulphonyl; More preferably select chlorine, nitro, methyl, trifluoromethyl or methyl sulphonyl for use; With

R ¹Be hydrogen; C ₁-C ₄Alkyl, preferable methyl; The fontanel element; Phenyl or substituted-phenyl;

R ²Be hydrogen or C ₁-C ₄Alkyl, preferable methyl; Or

R ¹And R ²Common is C ₂-C ₅Alkylidene group;

R ³Be hydrogen; C ₁-C ₄Alkyl, preferable methyl; Phenyl or substituted-phenyl, its condition is R ¹And R ³It not all is the phenyl of phenyl or replacement;

R ⁴Be hydrogen or C ₁-C ₄Alkyl, preferable methyl;

R ⁵Be hydrogen, fontanel element or C ₁-C ₄Alkyl, preferable methyl

R ⁶Be fontanel element, nitro, cyano group, trifluoromethyl ,-C(0)-OR ^f, R wherein ^fBe C ₁-C ₄Alkyl;-C(0) NR ^b ₂, the R here ^bBe hydrogen or C ₁-C ₂Alkyl; With

R ⁷And R ⁸Be respectively:

(1) hydrogen; (2) fontanel element, preferred chlorine, fluorine or bromine; (3) C ₁-C ₄Alkyl, preferable methyl, (4) C ₁-C ₄Alkoxyl group, preferred methoxyl group; (5) trifluoromethoxy; (6) cyano group; (7) nitro; (8) C ₁-C ₄The fontanel substituted alkyl is more preferably selected trifluoromethyl for use; (9) R ^bSOn-, wherein: n is an integer 0,1 or 2, and is preferred 2, and R ^bBe:

(a) C ₁-C ₄Alkyl, preferable methyl;

(b) be the C that fontanel element or cyano group replace ₁-C ₄Alkyl is preferentially selected chloromethyl for use, trifluoromethyl or cyano methyl;

(c) phenyl; Or

(d) benzyl;

(10)-NR ^cR ^d, R ^cAnd R ^dBe hydrogen or C independently ₁-C ₄Alkyl;

(11) R ^eC(0)-, R ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group;

(12)-SO ₂NR ^cR ^d, the R here ^cAnd R ^dDefinition the same; Or

(13)-N(R ^c) C(0) R ^d, the R here ^cAnd R ^dDefinition the same.

R ⁷Preferably be in 3, R ⁷Be hydrogen, chlorine, fluorine, trifluoromethyl, cyano group, C ₁-C ₄Alkoxyl group or C ₁-C ₄Better during alkylthio; R ⁷Be preferably hydrogen.R ⁸Preferably be in 4, R ⁸Be preferably fontanel element, cyano group, trifluoromethyl or R ^bSO ₂-, (R ^bBe C ₁-C ₄Alkyl, preferable methyl or C ₁-C ₄The fontanel substituted alkyl, preferred chloromethyl, difluoromethyl or trifluoromethyl).

Term " C ₁-C ₄Alkyl " comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.Term " fontanel element " comprises chlorine, bromine, iodine and fluorine.Term " C ₁-C ₄Alkoxyl group " comprise methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert.-butoxy.Term " C ₁-C ₄The fontanel substituted alkyl " comprise above-mentioned at C ₁-C ₄More such alkyl of definition in the alkyl,, one or more hydrogen is chlorine, bromine, iodine or fluorine replace.

The salt of above-claimed cpd (such as hereinafter definition) also at the row of scope of the present invention.

Because tautomerism, compound of the present invention can have following four kinds of structural formulas:

Wherein: R, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Definition the same.

In these four kinds of tautomers, the proton rather unstable of irising out on each tautomer, these protons are acids, and can remove by forming the anion salt with following four kinds of resonance forms with alkali reaction:

Wherein: R, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Definition the same.

The example of these base cations has: such as basic metal (as lithium, a sodium and potassium) class inorganic cation; With calcium and magnesium and so on alkaline-earth metal ammonium or such as being organic cation aliphatic series or the aromatic group ammonium, sulfonium, sulfur oxide or the phosphorus that replace.

When studying salt of the present invention, those skilled in the art will be appreciated that, can have in various degree association according to said cationic character between this anionoid and positively charged ion.Have as copper and so under suitable anionic some occasion, said salt can exist with chelated forms.

The compound and the salt thereof of invention are the universal active weedkiller of a class, and promptly they all have the deweeding effect for a variety of plants.Control of the present invention does not need the method for plant to comprise that above-claimed cpd or its salt with the deweeding significant quantity impose on the zone that needs controlling weeds.

Compound of the present invention can adopt following two steps or (if required) universal method preparation of three steps.

Shown in reaction (1), this law is set about from producing the enol ester intermediate.Shown in reaction (2), utilize the enol ester transformation to obtain the finished product, or if required, shown in reaction (3), will in (2) step, obtain product subsequently and give fontanelization.

This law reaches with respect to carrying out under the condition of the excessive one mole of irenine of said enol ester in the presence of catalytic amount, cyanide anion ion and/or cyaniding hydrogen source.

Reaction (1) and (2) can adopt the method for fractional steps to carry out, and promptly carries out step (2) with traditional method again with said enol ester separation with after reclaiming, or add cyanide source in this reaction medium after said enol ester forms; Or undertaken by single stage method, cyanide source promptly just mixes when reaction (1) beginning.

Wherein: R-R ^RThe same with the definition of irenine, Y is the fontanel element, (preferred chlorine), C ₁-C ₄Alkyl-C(0)-O-, C ₁-C ₄Alkoxy-C-(0)-O-or

The R of this group, R ⁷And R ⁸Definition and above-mentioned reactant in identical.The definition of irenine is the same, preferred three-C ₁-C ₆Alkylamine, alkaline carbonate or alkali-metal phosphoric acid salt.

General use one mole or excessive said alkali and the said diketone of molar weight and the benzoyl reagent of replacement is added in these two kinds of reagents as in the organic solvents such as methylene dichloride, toluene, ethyl acetate or dimethyl formamide in step (1).Preferably alkali or benzoyl reagent are added in the reaction mixture while cooling off.Stirring this reaction mixture down in 0 ℃ finishes substantially until reaction.

^*Be cyanide source; Gentle R-R in the reaction formula ⁸Definition the same.

In this step (2), the irenine and 0.01 of one mole enol ester intermediate and 1 to 4 mole is reacted to about cyanide source more than 0.5 mole or 0.5 mole, the preferable amount of said irenine is about 2 moles, about 0.01 to 0.1 mole of the preferred amount ranges of said cyanide source.In below 50 ℃, be preferably under 20 ° to the 40 ℃ left and right sides temperature, in reactor, stir this reaction mixture and carry out fully until rearrangement, reclaim the product that desire is wanted by traditional method again.

Some compound of the present invention also can prepare by following reaction:

Wherein: R, R ¹, R ², R ³, R ⁴, R ⁵, R ⁷And R ⁸Define the same, R ⁶It is halogen.

In step (3), generally be with one mole of 2-(2-substituted benzoyl)-1, the 3-cyclohexanedione is dissolved in such as in methylene dichloride one kind solvent.In order to prepare 1, have the compound of 1-3 halogen on 4 or 6 of 3-cyclohexanedione part, as the extraneous cooling conditions that suits of this class of ice-isopropanol bath under, have solvent or solvent-free in the presence of 1 to 3 mole of halogenating agent such as bromine of adding.The halogenic substituent that an institute of every increase desire is wanted will use one mole halogenating agent more.Also want halogenation R ¹Or R ⁵The time, these groups in the parent compound must be hydrogen.Under room temperature, this reaction mixture was stirred 1-8 hour then.Use the conventional process product.

Term " cyanide source " refers to a kind of like this or a class material, and this material is formed or produced prussic acid and/or cyanide anion ion by prussic acid and/or cyanide anion ion under rearrangement condition.

Preferred cyanide source has: such as sodium cyanide and this class alkali metal cyanide of potassium cyanide; Its moieties has methyl alkyl ketone cyanhydrin class such as the acetone cyanohydrin or the methyl iso-butyl ketone (MIBK) cyanhydrin of 1-4 carbon atom, benzaldehyde cyanhydrin; C ₂-C ₅The aliphatic aldehyde cyanhydrin is as acetaldehyde cyanhydrin, propionic aldehyde cyanhydrin etc.; The pimelinketone cyanhydrin; Lactonitrile; Zinc cyanide; Two and three (low alkyl group) silicomethane prussiate, particularly dimethyl and trimethylsilyl cyanide; The Tripotassium iron hexacyanide; And prussic acid itself.The advantage that it is believed that prussic acid is maximum, because the reacting phase that it produces is when rapid, price is also cheap.In these cyanalcohols, acetone cyanohydrin is preferred cyanide source.

This cyanide source consumption reaches 50 moles of % of said enol ester approximately.When reacting on a small scale, its consumption is low to moderate about 1 mole of %, and the speed of reaction that produces about 40 ℃ still can; For larger reaction, provide the reasonable result of circulation ratio during catalyst levels level high slightly (about 2 moles of %).In general, the preferable amount of cyanide source is about 1-10 mole %.

With respect to said enol ester, carrying out this reaction will be with excessive 1 mole irenine.Term " irenine " refers to such material, its effect is as alkali, and it is as the intensity of alkali or active in as oxyhydroxide quasi-alkali (can cause that said enol is esterolytic) with such as N, between the accelerine class weak base (can not bring into play useful effect).The irenine of Shi Yonging comprises organic bases and mineral alkali in this embodiment, organic bases such as trialkylamine, for example triethylamine; Mineral alkali such as alkaline carbonate and phosphoric acid salt.Suitable mineral alkali comprises yellow soda ash and tertiary sodium phosphate.

Said alkali is about the 1-4 mole with respect to the consumption of every mole of enol ester, about 2 moles of preferred amounts.

Cyanide source is certain alkali metal cyanide, especially during potassium cyanide, can comprise phase-transfer catalyst in the reaction, and crown ether is optimum phase-transfer catalyst.

Suitable usefulness solvent in the method is diversified, adopts the sort of solvent actually, is decided by the character of acyl group fontanel or acylate.1, the 2-ethylene dichloride is the preferred solvent of said reaction.Other useable solvents of reagent or product decision comprises thus: toluene, acetonitrile, methylene dichloride, ethyl acetate, dimethyl formamide and mibk (MIBK).

Generally speaking, the temperature of resetting is by the decision of the character of reagent and cyanide source, can reach about 50 ℃.

Above-mentioned substituted benzoyl chloride can be prepared by corresponding substituted benzoic acid by the method that L.F.Fieser and M.Fieser are introduced in organic synthesis reagent [1 volume, 767-769 page or leaf (1967)].

Wherein: R, R ⁷And R ⁸Definition the same.

And said substituted benzoic acid can be compiled carboxylic acid and esterification (The Chjemistry of Carboxylic acid and Ester) (J.Wiley and sons by S.Patai, New York, N, and C.A.Buehler and D.F.Pearson Y.(1969)], the various universal method preparations of in organic synthesis comment (Survey of organic Synthesis, J.Wileyand Sons(1970), introducing.

Below a), b) and c) be three representative examples in the methods described herein:

Wherein: R, R ⁷And R ⁸Definition the same.

In reaction (a), in aqueous sulfuric acid, will replace benzonitrile reflux several hours.Cool off this mixture, reaction product is separated with general method.

Wherein: R, R ⁷And R ⁸Definition the same.

In reaction (b), in aqueous hypochlorite solution, with the acetylbenzene reflux that replaces several hours, cooling mixture, reaction product is separated with general method.

Wherein: R, R ⁷With ⁸The definition of R is the same.

In reaction (c), replacement toluene reflux several hours in potassium permanganate solution, filter this solution then, use the general method reaction product isolated.

Above-mentioned replacement 1, the 3-cyclohexanedione can be by modern synthesis [second edition, the 7th chapter, H.O.House, W.A.Benjamin, Inc., Menlo Park, and the method for being introduced in the Li Bixishi chemistry yearbook (Liebigs Ann.Chem.) [679,9(1964)] (Von Hans Machleidt and Valentine Hartmann) preparation CA(1972)].

Following embodiment has introduced the synthetic of the representational compound of the present invention.

Embodiment 1

5,5-dimethyl-4-fluoro-2-(2-nitro-4-trifluoromethyl benzoyl) hexanaphthene-1,3-diketone triethylamine salt

Under the room temperature,, 5-dimethyl-4-fluoro-1,3-cyclohexanedione [0.5g, 0.0032 mole, press Leibigs Ann.Chem., 679, the method preparation of introducing in 9(1964)] and 0.25g(0.0032 mole with 5) pyridine is dissolved in the 20ml methylene dichloride.Slowly add the 2-nitro-4-trifluoromethyl benzoyl chloride (1.0g that is dissolved in the 20ml methylene dichloride while cooling off, 0.0039 mole), stirred this reaction mixture 24 hours under the room temperature, wash with water then twice, the saturated sodium bicarbonate aqueous solution washing once, water washing once, behind the venting water, organic phase Mg SO ₄Drying, revaporization obtain intermediate enol ester 5,5-dimethyl-6-fluoro-3-(2-nitro-4-trifluoromethyl benzoyloxy) hexamethylene 2-ketenes.With 5,5-dimethyl-6-fluoro-3-(2-nitro-4-trifluoromethyl benzoyloxy) hexamethylene-2-ketenes once all is dissolved in 30ml acetonitrile and triethylamine 0.7g, 0.007mol) in, then add again acetone cyanohydrin (0.05g, 0.0006mol).Stirred this solution 24 hours, and boiled off solvent, resistates obtains said product after the ether washing.

Embodiment 2

2-(2-chloro-4-methylsulfonyl benzoyl)-and hexanaphthene-1, the 3-diketone

Under the room temperature, in the 200ml methylene dichloride, dissolve 1, the 3-cyclohexanedione (11.2g, 0.1mol) and 2-chloro-4-methylsulfonyl Benzoyl chloride (23.3g, 0.1mol), slowly add triethylamine (11g while cooling off, 0.11mol), this reaction mixture was at room temperature stirred 5 hours, then in the hydrochloric acid of impouring 2N, venting water, organic phase Mg SO ₄Drying obtains intermediate enol ester 3-(2-chloro-4-methylsulfonyl benzoyloxy through evaporation again) hexamethylene-2-ketenes.With 3-(2-chloro-4-methylsulfonyl benzoyloxy) hexamethylene-2-ketenes be dissolved in immediately the 200ml acetonitrile that adds and triethylamine (22g, 0.22mol) in, then add acetone cyanohydrin (0.8g, 0.01mol).Stir this solution after 5 hours, in its impouring 2N hydrochloric acid, use twice of ethyl acetate extraction.Organic layer Mg SO ₄Drying boils off solvent and obtains said product.

Embodiment 3

4-bromo-2-(2-chloro-4-methylsulfonyl benzoyl)-and cyclohexyl-1, the 3-diketone

With 2-(2-chloro-4-methylsulfonyl benzoyl)-hexanaphthene-1; (6.6g 0.02mol) is dissolved in the 50ml methylene dichloride 3-diketone, after this solution is used for the cooling of ice-isopropanol bath; wherein drip in 75 minutes introversions and to be dissolved with bromine (2.9g, methylene dichloride 0.018ml) (50ml) solution.Finish, under room temperature, this reaction mixture was stirred 2 hours again.The semi-solid product wanted to obtain the 8.5g desire of this reaction mixture of concentrating under reduced pressure then.Identify with nuclear magnetic resonance spectrum, infrared spectra and mass spectroscopy.Available column chromatography is further purified product.

Some compound of selecting that can prepare by step noted earlier is listed in the table below, and for each compound a numbering is arranged all, and these numberings are suitable equally in the application's other parts.

(a) prepare at embodiment 3; (b) with the preparation of the form of triethylamine salt.

The deweeding shaker test

As mentioned above, the compound of producing as stated above described here is a plant toxicity compound, and they can adopt and have value in the various plants control.Selected The compounds of this invention is tested as follows as weedkiller.

Deweeding test before sprouting: handled preceding ten days; seven kinds of different weeds seeds are planted in loamy sand is arranged in lines along dish length; every row kind of a kind of seed, used grass seed has: Herba Setariae Viridis (FT) (Setaria Viridis); wetland grass (WG) (Echinochloa crusgalli); wild avena sativa (WO) (Avena fatua); annual morning glory (AMG) (lpomoea lacunosa); Tong fiber crops (VL) (Abutilon theophrasti); mustard (MD) (Barassica juncea) and yellow nutsedge(YNG) (Cyperus esculentus).Every row sowing sufficient seed grows 20-40 strain seedling after making sprouting according to the plant size.

On a glassine paper of weighing, take by weighing the compound 600mg that will test with analytical balance, paper and the compound that takes by weighing are placed in the wide-necked bottle (60ml) of a cleaning, with 40ml acetone or substitute dissolution with solvents.Shift this solution of 18ml in the wide-necked bottle of 60ml cleaning, for obtaining finally being the 0.5%(volume/volume) solution, with the mixture of forming by water and acetone that contains q.s polyoxyethylene sorbitol mono-laurate emulsifying agent (19: 1,22ml) dilute.Is 80 gallon/acre (748 liters/hectare) to make it spray amount with this solution spray by calibrated linearity spraying table on the dish of having sowed.Applicating ratio is 4 pounds/acre (4.48kg/ hectares).

After the processing, it is in 70-80 the greenhouse and spray water that dish is put in temperature.Two weeks after treatment is caused injury or prevents and treats degree by comparing to measure with undressed control plant of the same age.Write down the situation of causing injury of each plant by the percentage inverse amplification factor, its evaluation value is 0-100%, and 0% expression is not caused injury, and 100% expression suppresses fully.These test-results are listed in the table below in the II.

Sprout back deweeding test: this testing sequence and sprout before deweeding test identical, but to the processing of seven kinds of different weed seeds of being planted kind after carried out in 10-12 days.In addition, water for the dish of handling and only limit to soil surface, must not water on the leaf of germination plant.

Deweeding test-results after the sprouting is listed in the table below in the III.

Compound of the present invention and salt thereof are suitable for doing weedkiller to be used, and can use in different ways under various concentration.In fact consider that the preparation of a poisonous substance or its use-pattern may influence the material activity in certain given purposes, therefore the said compound and the salt of deweeding significant quantity, mix by auxiliary agent or the carrier that adopts usually with being convenient to agricultural dispersed activity composition, make Herbicidal combinations.Like this, these active deweeding compounds or salt can be made the sizable granule of granularity, wettable pulvis and missible oil.

The preceding deweeding of sprouting of multiple weeds is tested

At applicating ratio is that 1 pound/acre (1.12kg/ hectare) estimates several compounds down to the preceding activity of herbicide of sprouting of multiple weeds.

Deweeding was tested before this law was substantially similar to above-mentioned sprouting, but test compound only weighs up 150mg, and applicating ratio is 40 gallon/acre.

There is not red lamb's-quarters (PW) in this test, but several weeds below having increased:

Grass: cheatgrass brome (Bromus tectorun) (DB)

Italian ryegrass (Lolium multiflorun) (ARG)

Schrock (Sorghm bicolor) (SHC)

Daubentonia fiber crops (Sesbania exaltata) (SESB)

Black nightshade (Solanum sp) (SP)

Siberian cocklebur (Xanthiun SP) (CB)

Applicating ratio is that the test-results of 1.12kg/ hectare is listed in the table below in the IV.

Deweeding test after the sprouting of multiple weeds

At applicating ratio is activity of herbicide after 1 pound/acre (1.12kg/ hectare) descends several compounds of evaluation to the sprouting of the multiple weeds of use during multiple deweeding is tested before sprouting.

Generally speaking, this law is similar to deweeding test after the above-mentioned sprouting, but only weighing the 150mg test compound, applicating ratio is 40 gallon/acre.

Applicating ratio is that the test-results of 1.12kg/ hectare is listed in the table below in the V.

Not test (N.T.) represented in dash in the table.

The suitable herbicide of doing of compound of the present invention and salt thereof uses, and can use these compounds and salt thereof with various concentration by variety of way. Consider that poisonous substance preparation and the method for application used may affect activity of materials in certain given purposes, in fact said compound or the salt of deweeding effective dose, by be convenient to the normally used auxiliary agent of agricultural dispersed activity composition and carrier and mix, make Herbicidal combinations. So these active deweeding compounds or salt can be mixed with the sizable granule of granularity, wettable powder, missible oil, pulvis, suspending agent, solution or any other known dose of shape according to required method of application. Weighing scale, the contained active ingredient of these preparations can hang down and reach about 0.5% to up to more than about 95% or 95%. Character according to the seed that will give control or plant determines effective deweeding amount, and applicating ratio does not wait from about 0.01 to about 10 pounds/acre, and preferable range is about 0.02 to 4 pound/acre.

Wettable powder is the finely divided particle that is easy to be dispersed in water or other dispersant, at last with the wettable powder of this kind with dry powder doses be scattered in water or other liquid in dispersion be applied to soil. It then is the typical carriers of wettable powder that bleaching earth, kaolin, silica and other are easy to moistening organic or inorganic diluent. Usually wettable powder is mixed with and contains 5-95% left and right sides active ingredient, and be easy to moistening and dispersion, generally also contain a small amount of wetting agent, dispersant or emulsifying agent.

Missible oil is the homogeneous liquid composition that is dispersed in water or other dispersant, and can be fully formed by active ingredient or salt and liquid or solid emulsifying agent, also can contain liquid-carrier such as dimethylbenzene, heavy aromatic naphtha *, isophorone and other fixedness organic solvent. Do deweeding, these missible oil are dispersed in water or other liquid-carrier, and generally adopt Sprayable that it is imposed on the zone that will give processing. By weight, the percentage of main active ingredient changes with the method for application that will use composition, but generally speaking by weight the time said Herbicidal combinations contain active ingredient and be 0.5% to 95%.

The granular preparation that poisonous substance is stated from the suitable coarse granule generally directly is applied to the place, place that wish suppresses plant without dilution. The representative carrier of granular preparation has: sand, bleaching earth, Attagel, bentonite, imvite, vermiculite, perlite and other absorb poisonous substance or organic or inorganic matter that can the coated poisonous substance Matter. Generally granular preparation is made and contained 0.1% to 25% left and right sides active ingredient, wherein can contain surfactant, such as the heavy aromatic naphtha, kerosene or other petroleum distillate, or vegetable oil; And/or sticker, such as dextrin, glue or synthetic resin.

Typical wetting agent, dispersant or the emulsifying agent that uses in Agrotechnical formulation comprises such as alkyl or alkyl aryl sulfonate and sulfuric ester and salt thereof; Polyalcohol; Polyethoxylated alcohols; The surfactant of ester and aliphatic amine and other type, many above-mentioned substances can have been bought from the market. If the use surfactant, then the content in Herbicidal combinations is 0.1% to 15% by weight.

Pulvis is the mixture of free-pouring, active ingredient and tiny solid, and said tiny solid such as talcum, clay, flour and other are as the dispersant of said poisonous substance and the organic and inoganic solids of carrier, and pulvis is the suitable preparation that mixes usefulness with soil.

The paste that is used for some specific use is that the tiny solid poisonous substance is in the unit for uniform suspension of liquid-carrier such as water or oil. By weight, these preparations generally contain the active ingredient about 5%-95%, and for for the purpose of promote disperseing, also can contain a small amount of wetting agent, dispersion or emulsifying agent. When using, this class paste generally also will dilute, and with Sprayable it is applied to the zone of weeds infringement.

Be suitable for other preparation that deweeding uses and comprise the simple solution of active ingredient in dispersant, active ingredient fully dissolving under desired concn in this solution, said dispersant such as acetone, alkanisation naphthalene, dimethylbenzene and other organic solvent. Also can adopt the pressure atomization agent, smoke agent is typically arranged, wherein owing to the result of low boiling dispersant solvent carrier (such as freon) volatilization, active ingredient is dispersed with the form of tiny dispersion.

Available conventional method is applied to phytotoxic composite of the present invention on the plant. For example, with power duster, wide cut and hand sprayer and duster pulvis and fluid composition are applied on the plant. Because it is also effective when dosage is very low, thus available air-dusting or spraying, or with inhaling medicine rope (Rope Wick) dispenser. For a change or the seed of suppress growing or the growth of the seedlings of cereal crops, can pulvis or fluid composition be applied in the soil by conventional method as typical example, and it can be distributed in the soil that the following degree of depth in the face of land reaches 1/2 inch at least. Because this class phytotoxic composite equally also can only be sprayed on soil surface with the method for spraying or spray, so not necessarily must be with mechanical means with it Mixing with soil particle can not. Also phytotoxic composite of the present invention can be added to and be sent in the irrigation water that to process the field. This application process can make composition be absorbed by soil along with irrigation water and be penetrated in the soil. Availablely be scattered under the soil surface such as round disk rake is ploughed, raked the soil level or married operation one class commonsense method will impose on soil table dust composition, granule composite or liquid preparation. In following each example, said deweeding compound can replace with the deweeding salt of this compound.

Cream preparation

General component and content range particular components

Deweeding compound 5-55 deweeding compound 24

Surfactant (multiple) 5-55 oil-soluble sulfonic acid

Ester and polyoxy

Solvent (multiple) 20-90

100%

Vinethene

The suitable mixing

Thing 10

Polar solvent 27

Petroleum hydrocarbon 39

100%

Wettable powder

Deweeding compound 3-90 deweeding compound 80

Wetting agent 0.5-2 dialkyl group sodium naphthalene sulfonate 0.5

Dispersant 1-8 sodium lignin sulfonate 7

Diluent (multiple) 8.5-87 Attagel 12.5

100%    100%

The granule of extruding

Deweeding compound 1-20 deweeding compound 10

Bond 0-10 lignosulfonates 5

Diluent (multiple) 70-99 calcium carbonate 85

100%    100%

Suspending agent

Deweeding compound 20-70 deweeding compound 45

Surfactant (multiple) 1-10 APEO 5

Suspending agent (multiple) 0.05-1 Attagel 0.05

Antifreezing agent 1-10 propane diols 10

Antimicrobial 1-10 1,2-benzisothiazole 0.03

Antifoaming agent 0.1-1 quinoline-3-ketone

Solvent 7.95-77.85 silicon defoamer 0.02

Water 39.9

100%    100%

As making the active ingredient of Herbicidal combinations of the present invention with salt, the most handy those suitable agricultural salt.

Phytotoxic composite of the present invention also can contain other additive, and for example chemical fertilizer, other herbicide and other bactericide, these additives be as auxiliary agent, or combines use with above-mentioned arbitrary auxiliary agent. Be suitable for the chemical fertilizer that uses altogether with said active ingredient, such as ammonium nitrate, urea and calcium superphosphate.

Claims (14)

1, the following compound or its salt of general formula,

In the formula

R is the fontanel element, C ₁-C ₂Alkyl, C ₁-C ₂The alkoxyl group trifluoromethoxy, difluoro-methoxy, nitro, cyano group, C ₁-C ₂Fontanel substituted alkyl or R ^αSO _n(wherein n is 0 or 2 and R to-Ji ^αBe C ₁-C ₂Alkyl, trifluoromethyl or difluoromethyl,

R ¹Be hydrogen, C ₁-C ₄Alkyl, fontanel base, phenyl or substituted-phenyl,

R ²Be hydrogen or C ₁-C ₄Alkyl, perhaps

R ¹And R ²Connect together and be C ₂-C ₅Alkylidene group;

R ³Be hydrogen, C ₁-C ₄Alkyl, phenyl or substituted-phenyl, but condition is R ¹And R ³Can not be both phenyl or substituted-phenyl;

R ⁴Be hydrogen or C ₁-C ₄Alkyl;

R ⁵Be hydrogen, fontanel element or C ₁-C ₄Alkyl;

R ⁶Be fontanel element, cyano group, nitro, trifluoromethyl ,-C (O)-OR ^f(R ^fBe C ₁-C ₄Alkyl) or-C (O) NR ^b ₂(R ^bBe hydrogen or C ₁-C ₂Alkyl),

R ⁷And R ⁸Be (1) hydrogen independently of one another; (2) fontanel element, (3) C ₁-C ₄Alkyl; (4) C ₁-C ₄Alkoxyl group; (5) trifluoromethoxy; (6) cyano group; (7) nitro; (8) C ₁-C ₄The fontanel substituted alkyl; (9) R ^b(wherein n is integer 0,1 or 2 to SOn-, R ^bBe (a) C ₁-C ₄Alkyl, (b) C of fontanel element or cyano group replacement ₁-C ₄Alkyl, (c) phenyl or (d) benzyl), (10)-NR ^cR ^d(R wherein ^cAnd R ^dBe hydrogen or C independently of one another ₁-C ₄Alkyl); (11) R ^eC (O)-(R wherein ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group; Or (12)-SO ₂NR ^cR ^d(R wherein ^cWith

R ^dDefinition the same) and (13)-N (R ^c) C (O) R ^d(R wherein ^cAnd R ^dDefinition the same).

2, the compound of claim 1, R is the chlorine bromine in the general formula, methyl, methyl oxygen base, nitro, trifluoromethyl or methylsulfonyl; R ¹, R ², R ³, R ⁴And R ⁵Be hydrogen or methyl; R ⁶Be the plain R of fontanel ⁷And R ⁸Be (1) hydrogen independently of one another; (2) fontanel element; (3) C ₁-C ₄Alkyl; (4) C ₁-C ₄Alkoxyl group; (5) trifluoromethoxy; (b) cyano group; (7) nitro; (8) C ₁-C ₄The fontanel substituted alkyl; (9) R ^bSOn(wherein n is integer 0,1 or 2, R ^bBe (a) C ₁-C ₄Alkyl; (b) C of fontanel element or cyano group replacement ₁-C ₄Alkyl, (c) phenyl or (d) benzyl); (10)-NR ^cR ^d(R wherein ^cAnd R ^dBe hydrogen or C independently of one another ₁-C ₄Alkyl); (11) R ^eC(0)-(R wherein ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group; (12) SO ₂NR ^cR ^d(R wherein ^cAnd R ^dDefinition the same); Or (13)-N-(R ^c) C(0) R ^d(R wherein ^cAnd R ^dDefinition the same).

3, the compound of claim 2, R in the general formula ⁷And R ⁸Independently be hydrogen, fluorine, chlorine, bromine, methyl separately, C ₁-C ₄Alkoxyl group, trifluoromethoxy, cyano group, nitro, trifluoromethyl, R ^bSOn-(wherein n is integer 0 or 2, R ^bBe methyl, chloromethyl, trifluoromethyl), ethyl or n-propyl) and, R ^eC(0)-(R wherein ^eBe C ₁-C ₄Alkyl) or SO ₂NR ^cR ^d(R wherein ^cAnd R ^dDefinition the same), and R ⁷Be on the 3-position and R ⁸Be on the 4-position.

4, a kind of method of preventing and treating unwanted plant, this method comprise that the compound or its salt that the general formula of effective amount of herbicide is following is applied to the zone of the anti-treatment of needs;

In the formula

R is the fontanel element, C ₁-C ₂Alkyl, C ₁-C ₂Alkoxyl group, trifluoromethoxy, difluoro-methoxy, nitro, cyano group, C ₁-C ₂The fontanel substituted alkyl, R ^a(wherein n is 0 or 2 to the SOn-base, R ^aBe C ₁-C ₂Alkyl, trifluoromethyl or difluoromethyl);

R ¹Be hydrogen, C ₁-C ₄Alkyl,, fontanel element, phenyl or substituted-phenyl,

R ²Be hydrogen or C ₁-C ₄Alkyl, perhaps

R ¹And R ²Connect together and represent C ₂-C ₅Alkylidene group;

R ³Be hydrogen, C ₁-C ₄Alkyl, phenyl or substituted-phenyl, but condition is R ¹And R ³Can not be all the phenyl of phenyl or replacement;

R ⁴Be hydrogen or C ₁-C ₄Alkyl;

R ⁵Be hydrogen, fontanel element or C ₁-C ₄Alkyl;

R ⁶Be fontanel element, cyano group, nitro, trifluoromethyl ,-C(0)-OR ^f(R ^fBe C ₁-C ₄Alkyl) or-C(0) NR ^b ₂(R ^bBe hydrogen or C ₁-C ₂Alkyl)

R ⁷And R ⁸Be (1) hydrogen independently of one another; (2) fontanel element, (3) C ₁-C ₄Alkyl; (4) C ₁-C ₄Alkoxyl group; (5) trifluoromethoxy; (6) cyano group; (7) nitro; (8) C ₁-C ₄The fontanel substituted alkyl; (9) R ^bSOn-(wherein n is integer 0,1 or 2, R ^bBe (a) C ₁-C ₄Alkyl, (b) C of fontanel element or cyano group replacement ₁-C ₄Alkyl, (c) phenyl or (d) benzyl), (10)-NR ^cR ^d(R wherein ^cAnd R ^dBe hydrogen or C independently of one another ₁-C ₄Alkyl); (11) R ^eC(0)-(R wherein ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group; Or (12)-SO ₂NR ^cR ^d(R wherein ^cAnd R ^dDefinition the same); Or (13)-N(R ^c) C(0) R ^d(R wherein ^cAnd R ^dDefinition the same).

5, the method for claim 4, R is a chlorine in the general formula, bromine, methyl, methoxyl group, nitro, trifluoromethyl or methylsulfonyl; R ¹, R ², R ³, R ⁴And R ⁵Be hydrogen or methyl; R ⁶Be the fontanel element, R ⁷And R ⁸Be (1) hydrogen independently of one another; (2) fontanel element, (3) C ₁-C ₄Alkyl; (4) C ₁-C ₄Alkoxyl group; (5) trifluoromethoxy; (6) cyano group; (7) nitro; (8) C ₁-C ₄The fontanel substituted alkyl; (9) R ^bSOn-(wherein n is integer 0,1 or 2, R ^bBe (a) C ₁-C ₄Alkyl, (b) C of fontanel element or cyano group replacement ₁-C ₄Alkyl, (c) phenyl or (d) benzyl), (10)-NR ^cR ^d(R wherein ^cAnd R ^dBe hydrogen or C independently of one another ₁-C ₄Alkyl); (11) R ^eC(0)-(R wherein ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group; Or (12)-SO ₂NR ^cR ^d(R wherein ^cAnd R ^d-definition the same); Or (13)-N(R ^c) C(0) R ^d(R wherein ^cAnd R ^dDefinition the same).

6, according to the method for claim 5, wherein: R ⁷And R ⁸Be hydrogen, chlorine, fluorine, bromine, methyl, C independently ₁-C ₄Alkoxyl group, trifluoromethoxy, cyano group, nitro, trifluoromethyl, R ^bSOn-(n is integer 0 or 2, R ^bBe methyl, chloro methyl, trifluoromethyl, ethyl or n-propyl), R ^eC(0)-(R ^eBe C ₁-C ₄Alkyl) or SO ₂NR ^cR ^d(R ^cAnd R ^dDefinition the same), and R ⁷On three, R ⁸On four.

7, a kind of Herbicidal combinations, said composition contain the 2-(2-substituted benzoyl of activity of herbicide)-the 4-(replacement)-1,3-cyclohexanedione or its salt and a kind of inert support.

8, according to the Herbicidal combinations of claim 7, wherein, said 2-(2-substituted benzoyl)-4-(replaces)-1, the 3-cyclohexanedione is a compound:

And salt,

In said compound:

R is fontanel element, C ₁-C ₂Alkyl, C ₁-C ₂Alkoxyl group, trifluoromethoxy, difluoro-methoxy, nitro, cyano group, C ₁-C ₂Fontanel substituted alkyl, R ^aSOn-(n is 0 or 2, R ^aBe C ₁-C ₂Alkyl), trifluoromethyl or difluoromethyl;

R ¹Be hydrogen, C ₁-C ₄Alkyl, fontanel element, phenyl or substituted-phenyl,

R ²Be hydrogen or C ₁-C ₄Alkyl, or

R ¹And R ²Common is C ₂-C ₅Alkylidene group,

R ³Be hydrogen, C ₁-C ₄Alkyl, phenyl or substituted-phenyl, its condition are R ¹And R ³Not all be phenyl or substituted-phenyl,

R ⁴Be hydrogen or C ₁-C ₄Alkyl,

R ⁵Be hydrogen, fontanel element or C ₁-C ₄Alkyl,

R ⁶Be fontanel element, cyano group, nitro, trifluoromethyl ,-C(0)-OR ^f(R wherein ^fBe C ₁-C ₄Alkyl) or-C(0) NR ^b ₂(the R here ^bBe hydrogen or C ₁-C ₂Alkyl),

R ⁷And R ⁸Be independently: (1) hydrogen, (2) fontanel element (3) C ₁-C ₄Alkyl (4) C ₁-C ₄Alkoxyl group (5) trifluoromethoxy (6) cyano group (7) nitro (8) C ₁-C ₄Fontanel substituted alkyl (9) R ^bSOn-, wherein: n is an integer 0,1 or 2, R ^bBe: (a) C ₁-C ₄Alkyl (b) is the C that fontanel element or cyanogen replace ₁-C ₄Alkyl, (c) phenyl, or (d) benzyl, (10)-NR ^cR ^d, R wherein ^cAnd R ^dBe hydrogen or C independently ₁-C ₄Alkyl; (11) R ^eC(0)-, R wherein ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group, or (12)-SO ₂NR ^cR ^d, R ^cAnd R ^dThe same and (13)-N(R of definition ^c) C(0) R ^dThe R here ^cAnd R ^dDefinition the same.

9, composition according to Claim 8, wherein: R is chlorine, bromine, methyl, methoxyl group, nitro, trifluoromethyl or methylsulfonyl,

R ¹, R ², R ³, R ⁴And R ⁵Be hydrogen or methyl,

R ⁶Be the fontanel element,

R ⁷And R ⁸Be independently: (1) hydrogen, (2) fontanel element (3) C ₁-C ₄Alkyl, (4) C ₁-C ₄Alkoxyl group, (5) trifluoromethoxy, (6) cyano group, (7) nitro, (8) C ₁-C ₄Fontanel substituted alkyl, (9) R ^bSOn-, wherein n is an integer 0,1 or 2, R ^bBe: (a) C ₁-C ₄Alkyl, (b) are the C that fontanel element or cyanogen replace ₁-C ₄Alkyl, (c) phenyl, or (d) benzyl, (10)-NR ^cR ^d, R wherein ^cAnd R ^dBe hydrogen or C independently ₁-C ₄Alkyl, (11) R ^eC(0)-, the R here ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group, or (12) SO ₂NR ^cR ^d, R ^cAnd R ^dDefinition the same, or (13)-N(R ^c) C(0) R ^d, R ^cAnd R ^dDefinition the same.

10, according to the composition of claim 9, wherein: R ⁷And R ⁸Be hydrogen, chlorine, fluorine, bromine, methyl independently, C ₁-C ₄Alkoxyl group, trifluoromethoxy, cyano group, nitro, trifluoromethyl, R ^bSOn-(n is integer 0 or 2, R ^bBe methyl, chloro methyl, trifluoromethyl, ethyl or n-propyl), R ^eC(0)-(R ^eBe C ₁-C ₄Alkyl) or SO ₂NR ^cR ^d(R ^cAnd R ^dDefinition the same), and R ⁷On three, R ⁸On four.

11, the method for the unwanted plant of control; said method comprises: Herbicidal combinations is imposed on the zone of desiring to add control; said Herbicidal combinations comprises the compound 2-(2-substituted benzoyl of activity of herbicide)-the 4-(replacement)-1,3-cyclohexanedione and salt thereof and inert support.

12, a kind of method for preparing compound and salt thereof, said compound is

In this compound:

R is fontanel element, C ₁-C ₂Alkyl, C ₁-C ₂Alkoxyl group, trifluoromethoxy, difluoro-methoxy, nitro, cyano group, C ₁-C ₄Fontanel substituted alkyl, R ^aSOn-(wherein n is 0 or 2, and R is C ₁-C ₂Alkyl), trifluoromethyl or difluoromethyl,

R ¹Be hydrogen, C ₁-C ₄Alkyl, fontanel element, phenyl or substituted-phenyl,

R ²Be hydrogen or C ₁-C ₄Alkyl or

R ¹And R ²Common is C ₂-C ₅Alkylidene group,

R ³Be hydrogen, C ₁-C ₄Alkyl, phenyl or substituted-phenyl, its condition are R ¹And R ³Not all be phenyl or substituted-phenyl,

R ⁴Be hydrogen or C ₁-C ₄Alkyl,

R ⁵Be hydrogen, fontanel element or C ₁-C ₄Alkyl,

R ⁶Be fontanel element, cyano group, nitro, trifluoromethyl ,-C(0)-OR ^f(R wherein ^fBe C ₁-C ₄Alkyl) or-C(0) NR ^b ₂(the R here ^bBe hydrogen or C ₁-C ₂Alkyl),

R ⁷And R ⁸Be independently: (1) hydrogen, (2) fontanel element, (3) C ₁-C ₄Alkyl, (4) C ₁-C ₄Alkoxyl group, (5) trifluoromethoxy, (6) cyano group, (7) nitro, (8) C ₁-C ₄Fontanel substituted alkyl, (9) R SOn-, wherein: n is an integer 0,1 or 2, R ^bBe: (a) C ₁-C ₄Alkyl (b) is the C that fontanel element or cyanogen replace ₁-C ₄Alkyl, (c) phenyl, or (d) benzyl, (10)-NR ^cR ^d, R wherein ^cAnd R ^dBe hydrogen or C independently ₁-C ₄Alkyl; (11) R ^eC(0)-, R wherein ^eBe C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group, or (12)-SO ₂NR ^cR ^d, R ^cAnd R ^dThe same and (13)-N(R of definition ^c) C(0) R ^dThe R here ^cAnd R ^dDefinition the same, said method comprises:

(a) under at least one mole of irenine existence condition, make compound (1) and compound (2) reaction form intermediate enol ester (3), said compound (1) is:

R in this compound (1) ¹To R ⁶Definition the same,

Said compound (2) is the benzoyl reagent that replaces,

In reagent (2): R, R ⁷And R ⁸Definition the same, Y is fontanel element, C ₁-C ₄Alkyl-C(0)-O-, C ₁-C ₄Alkoxy-C (0)-O-or group

R in this group, R ⁷And R ⁸The same reagent of definition (2) in identical,

Said intermediate enol ester (3) is

R to R in the mesosome enol ester (3) hereinto ⁸Definition the same,

(b) 1 mole of intermediate enol ester (3) is reacted with 1 to 4 mole of irenine and 0.01 to about cyanide source more than 0.5 mole or 0.5 mole and form compound

R in this compound ¹To R ⁸Definition the same.

13, according to a kind of method of claim 12, wherein: X is the fontanel element, and said irenine is three-C ₁-C ₆Alkylamine, pyridine, alkaline carbonate or alkali metal phosphate, and said cyanide source is alkali metal cyanide, methyl C ₁-C ₄Alkyl ketone cyanhydrin, phenyl aldehyde close or C ₂-C ₅Aliphatic aldehyde cyanhydrin, cyanalcohol, zinc cyanide, three (low alkyl group) silicomethane prussiate or prussic acid.

14, according to the method for claim 13, wherein X is that chlorine, said irenine are three-C-C alkylamine, pyridine, yellow soda ash or sodium phosphate, and said cyanide source is potassium hydride KH, acetone cyanohydrin or prussic acid.