JP2579663C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   The present invention relates to certain substituted cyclic dione compounds having herbicidal activity, a method for producing the same, and
And compositions containing the same.   Herbicide compositions containing cyclohexanedione coupled to an aryl group
For example, EP-A-90262, EP-A-137, 963, EP-A-135, 191 and EP-A-186, 119
It is described in.   According to the present invention, formula (I): Wherein X is oxygen or sulfur; Is the formula: (Where R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is a hydrogen or methyl group)
R; R¹Means up to 10 ring atoms (up to 3 of these ring atoms are selected from oxygen, nitrogen and sulfur)
A mono- or fused bicycloheterocycle containing
The ring is oxo, mercapto, halo, nitro, cyano, amino, mono or dialky
Ruamino, amide, C₁−C₆Alkyl, C_Two−C₆Alkenyl, C_Two−C₆Alkynyl, Si
Chloroalkyl, haloalkyl, haloalkoxy, aryl (fluorine, chlorine, bromine,
C₁−C₆Alkyl or C₁−C₆Optionally substituted with alkoxy), hydroxy,
Alkoxy, alkoxycarbonyl, alkylcarbonyl, mono- or dialkyi
Rucarbamoyl, alkylthio, alkylsulfinyl, alkylsulfonyl,
Sulfonamide, alkylcarbonyloxy, alkylcarbonylamino, pyri
Substituted by one or more groups selected from the group consisting of a jyl or thienyl group
Provided that when X is oxygen, R¹Is pyridyl, pyrimidinyl or
Is not a heterocyclic ring having two oxygen atoms linked to a benzene ring.]
Substituted cyclic dione compound or a salt thereof, enamine or an analog thereof, an acylate
, Sulfonate, carbamate or ether derivatives are provided.   Compounds of formula (I) may be in a number of tautomeric forms, for example, (Where R¹, X, X¹, X^TwoAnd Y have the same meaning as defined for formula (I)
Has) form. Y is X¹Or X^TwoAdjacent to the carbon atom carrying
Still other tautomers exist where they contain a hydrogen substituent on a carbon atom.
All such forms are within the scope of the present invention.   Compounds of formula (I) contain free hydroxyl or thiol groups in the manner described above.
If the compound is a salt thereof, particularly an agriculturally and horticulturally acceptable salt,
Or its analogs, acrylates, sulfonates, carbamates or ethers.
Can be induced.   Suitable agriculturally and horticulturally acceptable salts include sodium, potassium, calcium
And ammonium salts.   Examples of ammonium salts include the formula: N⁺R^cR^dR^eR^f (R in the formula^c, R^d, R^eAnd R^fAre each hydrogen and optionally for example hydroxyl
Substituted by a group_1-10Selected from alkyl groups)
You. R^c, R^d, R^eAnd R^fIs an optionally substituted alkyl group
If appropriate, they suitably contain from 1 to 4 carbon atoms.   Suitable acrylate or ether derivatives are those wherein the OH moiety is each of the formula: -O
COR^TwoOr -OR^Two(R^TwoIs optionally substituted, for example having 1 to 6 carbon atoms
A compound converted to an alkyl or aryl group, for example a phenyl group)
is there.   Suitable carbamate derivatives are those wherein the OH moiety is a group: Element or the aforementioned group R^TwoIs a compound that has been converted to   X, X¹And X^TwoIs preferably oxygen.   As used herein, the term "enamine or the like" refers to X or
Is X¹One of which is acid And the other is NR^ThreeR^Four, Halogen such as fluorine or SR^TwoReplaced by
Derivatives.   These derivatives can be manufactured by a conventional method.   R¹Is a mono- or fused bicycloheterocycle, as described above, and
It can be an aromatic or non-aromatic ring. R¹Contains up to 10 ring atoms.
Up to three of the offspring are selected from oxygen, nitrogen and sulfur.   R¹If is a monocyclic ring, this may be a heteroaryl having up to 7 ring atoms.
Suitably, it is a heteroaryl group, with up to three of these ring atoms being oxygen or nitrogen.
Selected from sulfur and sulfur. As used herein, a "heteroaryl group"
The term means aromatic heterocyclic.   R¹Is a fused bicyclic ring, one or both of the two rings have a heteroatom
And these rings may be represented by any of the groups:   Examples of such heterocyclic groups are furyl, thienyl, pyrrolyl, pyrazolyl
, Pyridyl, pyrimidinyl, imidazoyl, triazolyl, dithiol
, Oxathiol, isoxazolyl, oxazolyl, thiazolyl,
  Isothiazolyl, oxadiazolyl, thiodiazolyl, oxatriazo
Ryl, dioxazolyl, oxathiazolyl, oxathiol, dioxy
Nil, pyridazinyl, pyrazil, piperazinyl, priazinyl, o
Oxazinyl, isoxazinyl, oxathiazinyl, morpholinyl, aze
Pinyl, oxepinyl, thiepinyl, diazepinyl, benzofuranyl,
  Inbenzofuranyl, benzothienyl, isobenzothienyl, thionaph
Tarenyl, isothionaphthalenyl, indolyl, isoindolyl, in
Dazolyl, indoleninyl, iso Benzazolyl, pyranopyrrolyl, isoindazolyl, indoxazinyl,
  Benzoxazolyl, benzopyranyl, quinolinyl, isoquinolinyl,
Sinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, naphthyl
Dinyl, pyridopyridinyl, pyranyl, thiopyranyl, chromenil,
Thiachromenyl, benzoxazinyl, benzisoxazinyl and purine groups
No.   Heterocyclic group R¹Specific examples of frills, thiazolyl, thienyl,
Nnzoxazolyl, pyrazolyl, pyridazinyl, pyrazinyl and benzoxa
A zolyl group.   These heterocyclic groups are linked via a carbon atom or optionally via a nitrogen atom
Can be done.   A suitable heterocyclic group R¹Contains up to 10 and preferably up to 7 carbon atoms
.   Group R¹And R⁸Suitable substituents optionally present for are oxo,
For mercapto, fluoro, chloro, bromo or iodo Halo, nitro, cyano, amino, mono- or dialkylamino,
Mid, alkyl, alkenyl, alkynyl, cycloalkyl, trif
Haloalkyl, such as fluoromethyl, haloal, such as trifluoromethoxy
Optionally substituted aryl, such as coxy, phenyl or naphthyl,
Droxy, alkoxy, alkoxycarbonyl, alkylcarbonyl,
Mono- or dialkylcarbamoyl, alkylthio, alkylsulfinyl
, Alkylsulfonyl, sulfonamide, alkylcarbonyloxy,
Selected from alkylcarbonylamino or heterocyclic groups such as pyridyl and thienyl.
One or more groups may be mentioned.   These substituents have the group R¹To the carbon and / or nitrogen atoms.   Alkyl, alkenyl or alkenyl groups or moieties in the above substituents are from 1 to
It preferably contains 6 carbon atoms. Present when the aryl group
Suitable substituents include fluoro, Halo, such as chloro or bromo, C_1-6Alkyl or C_1-6Alkoxy groups include
It is.   In a preferred embodiment, R¹Is pyridyl, pyrimidinyl, pyridazinyl or
Is a 6-membered heteroaryl containing one or two nitrogen atoms, such as a pyrazinyl group
It is a ring.   In another preferred embodiment, R¹Is a 5-membered heteroaryl group or 5-membered
Contains a heteroaryl group.   For example, R¹Is a group of the formula: [Wherein, R^FiveIs hydrogen, C₁-C_FourAlkyl group, preferably C₁-C_TwoAn alkyl group, or
An optionally substituted aryl group such as a phenyl group;⁶, R⁷And R⁸
Are, respectively, (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine;₁-C
_Four(4) haloalkoxy group, preferably OCF_Three;(Five)
C₁-C_Four(6) cyano group; (7) nitro group; (8)
C₁-C_FourHaloalkyl group, preferably trifluoromethyl group; (9) R⁹SO_n-(In the formula
, N is an integer of 0, 1 or 2, preferably 2.⁹Is   (a) C₁-C_FourAn alkyl group, preferably a methyl group;   (b) halogen, cyano group, C₁-C_TwoAlkoxy Group or C₁-C_TwoC substituted with an alkylthio group₁-C_FourAn alkyl group, preferably
Lormethyl, difluoromethyl, trifluoromethyl or cyanomethyl groups;   (c) a phenyl group; or   (d) a benzyl group; (10) -NR^TenR¹¹(Where R^TenAnd R¹¹Is hydrogen or C₁-C_FourA
(11) R¹²C (O)-(wherein, R¹²Is C₁-C_FourAlkyl group or C
₁-C_Four(12) -SO_TwoNR^TenR¹¹(Where R^TenAnd R¹¹Is
Or (13) -N (R^Ten) C (O) R¹¹(Where R^TenAnd R¹¹Is
Which has the meaning described above).   In particular, R¹Is the formula: (Where R^FiveAnd R⁶Has the meaning described above).   In particular, R^FiveIs C, which may be linear or branched_1-6An alkyl group or phenyl
, P-chlorophenyl, p-methoxyphenyl or p-methylphenyl group
And a phenyl group which may have a substituent.   Preferred groups R⁶Is a haloalkyl group, especially a trifluoromethyl group.   According to yet another aspect, R¹Is the formula:[Wherein, R⁶, R⁷And R⁸Has the meaning described above, and R¹²Or R¹³Is one of = N-
And the other is C (R¹⁴) And R¹⁴Is a halogen such as hydrogen, chlorine, fluorine or bromine
C; such as a methyl group₁-C_FourAlkyl group; OCF_ThreeA C such as a methoxy group₁−
C_FourAlkoxy group; cyano group; nitro group; trifluoro C such as a rumethyl group₁-C_FourHaloalkyl group; R¹⁵SO_m(Where m is 0, 1 or
Is an integer of 2, preferably 2, and R¹⁵Is C such as a methyl group₁-C_FourAlkyl group
Is a group).   Further, R¹Is the formula: Wherein Z contains up to three heteroatoms selected from oxygen, sulfur and nitrogen;
Which is a 5- or 6-membered saturated or unsaturated fused ring). Ring Z is 2
It preferably contains one oxygen atom or an oxygen atom or a sulfur atom and a nitrogen atom.
Good. Therefore the group R¹As an example (Where R⁶Has the meaning described above).   Base: Is, as described above, a formula: It is a group of.   R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is hydrogen or C_1-4Alkyl groups, in particular,
C_1-2It is an alkyl group.   R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is most preferably a hydrogen or methyl group
preferable.   A particularly preferred group of compounds is of formula (IA): (Where R^{twenty five}Is an optionally substituted heteroaryl group;¹⁶, R¹⁷, R
²⁰And R^{twenty one}Has the meaning described above, provided that at least R¹⁶And R¹⁷Or R²⁰And R
^{twenty one}Are not hydrogen), or a salt or acid salt thereof.
Rate or sulfonate derivative.   R¹⁶, R¹⁷, R²⁰And R^{twenty one}Is C_1-4Alkyl groups, especially methyl groups, are preferred.
Good.   Examples of compounds of formula (I) are shown in Tables I and II.   The compound of formula (I) has the formula (II):(R in the formula¹, X, X¹And X^TwoHas the same meaning as defined in formula (I)
) In the presence of a cyanide (cyan ion) source and a mild base.
It can be manufactured by transferring.   The reaction is in the presence of an inert solvent such as acetonitrile, at -30 ° C to 90 ° C, preferably
Is suitably performed at a temperature of 20 ° C to 40 ° C.   Suitable sources of cyanide include salts such as sodium and potassium cyanide.
Lucali metal cyanide; acetone or methyl isobutyl ketone cyanohydrin
Of methyl alkyl ketone having 1 to 4 carbon atoms in the alkyl group
N-hydrin; such as cyanohydrin such as acetaldehyde and propionaldehyde
Sometimes benzaldehyde or C_Two−C_FiveAliphatic aldehyde cyanohydrin; Zinc cyanide; tri (lower alkyl) silyl cyanide, especially trimethylsilyl
Cyanide; and hydrogen cyanide itself.   A preferred cyanide source is acetone cyanohydrin.   The amount of the cyanide source used is sufficient to promote the reaction, for example, the formula (II)
1 to 50 mol%, preferably 1 to 10 mol% of the compound of   Suitable mild bases for use in the above reaction include organic acids such as tertiary amines.
Bases and inorganic bases such as alkali metal carbonates and phosphates. Appropriate
Examples of the tertiary amine include trialkylamines such as triethylamine and triethanolamine.
Trialkanolamines such as thiolamine and pyridine. Appropriate
Inorganic bases include potassium carbonate and trisodium phosphate.   The base is used in an amount of about 1-4 mol%, preferably about 2 mol% of the compound of formula (II)
It is appropriate to do so.   The compound of formula (I) has the formula (III):(X in the formula¹, X^TwoAnd Y have the same meaning as defined in formula (I)
And a compound of formula (IV):                 R¹CXZ (IV) (R in the formula¹And X have the same meanings as defined in formula (I), and Z is
(Which is a leaving group) in the presence of a base.   Suitable bases for use in the above reactions are those for use in the transfer of compounds of formula (II).
It is a mild base described. The preferred base is triethylamine.   Suitable leaving groups Z include halogen ions such as chloride ions.   The reaction is dichloromethane, 1,2-dichloroethane, Of inert organic solvents such as toluene, acetonitrile or dimethylformamide
It is suitably carried out in the presence at a mild temperature between 0 and 50 ° C., conveniently at room temperature.   The compound of formula (I) may also be a compound of formula (III) and a compound of formula (V):                 R¹CXOH (V) (Where R¹And X¹Has the same meaning as defined in formula (I))
With a dehydrating agent and a basic organic catalyst.   Suitable dehydrating agents include dicyclohexylcarbodiimide (DCC).
It is used in an amount of at least one molar equivalent of the compounds of formulas (III) and (V).
You.   Examples of suitable basic organic catalysts are 4-dimethylaminopyridine (DMAP) and 4
-Pyrrolidinopyridine (PPY).   The reaction is acetonitrile, tetrahydrofuran, dichloromethane, or 1,2-dichloromethane.
Rorethane It is suitably carried out in an inert organic solvent. Suitable temperature, e.g.
Preferably, ambient temperature may be used.   Alternatively, the compound of formula (I) can be obtained by combining the compound of formula (III) with a compound of formula (VI):                 R¹CXCN (VI) (Where R¹And X have the above-mentioned meaning) and the presence of a base and a Lewis acid
It can be produced by reacting under the following conditions.   Suitable bases are the mild bases mentioned for use in the transfer of compounds of formula (II) above.
It is.   Suitable Lewis acids are zinc chloride and aluminum trichloride, preferably zinc chloride.
You.   The reaction is carried out at -20 ° C in an organic solvent such as acetonitrile or methylene chloride.
Performed at a moderate temperature of ~ + 40 ° C.   Both zinc chloride and base are slightly excess with respect to the compounds of formulas (III) and (VI).
It is appropriate to use.   Compounds of formulas (III), (IV), (V) and (VI) Is a known compound or can be produced from a known compound by a conventional method.   For example, a specific example of a compound of Formula (V) is Formula (VA): (R in the formula^FiveAnd R⁶Has the meaning described above).   These compounds can be prepared as shown in Reaction Step A. Reaction process diagram A   Appropriate conditions for the first step in the reaction scheme A are described in R. Jones, JACS.73 Described in 3686
Have been.   The subsequent steps are outlined in GB 2.149,402A.   Particular examples of compounds of formula (III) are of formula (IIIA): Is a compound of   R¹⁶, R¹⁷, R²⁰And R^{twenty one}Is a methyl group or hydrogen, a compound of the formula (IIIA)
Construction is reported by Riedl and Risse (Justus Liebigs Annalen der Chem
ie, 1954,585, 209).   R¹⁶, R¹⁷, R²⁰And R^{twenty one}Are the same and C_1-4A compound of the formula (IIIA), which is an alkyl group:
Can be prepared according to the following reaction step B:Reaction process diagram B   In the above formula, X 'is a leaving group such as a halogen ion, particularly an iodine ion.
You. Suitable reaction conditions will be apparent from the literature. For example, the reaction process diagram
A suitable base for use in the first step of B is sodium methoxide in methanol.
It is. Acids suitable for use in the first step of Reaction Scheme B are inorganic acids such as hydrochloric acid
It is.   By adjusting the reaction conditions of the first step of the reaction, R²⁰And / or R^{twenty one}But
A compound of formula (IIIA), which is hydrogen, can be obtained.   Alternatively, the compound of formula (IIIA) can be Therefore, the method reported (Chem, Ber. 1959,92, 2033) or similar
It can be manufactured by the following method.   In this method, the compound of formula (IIIA) is a compound of formula (VII): Compound in an organic solvent such as methanol, such as sodium methoxide.
Sometimes, it can be produced by cyclization in the presence of a base. Compound of formula (VII) reacts
It can be manufactured by the method shown in the process chart C. Reaction process diagram C   The detailed conditions for each step in Reaction Scheme B depend on the particular compound used.
Variable and routine methods and appropriate literature could be determined.   The compound of formula (VIII) has the formula (IX): A compound of formula R²⁰A compound of X 'and optionally R^{twenty one}X 'compound and methanol
In the presence of a base such as sodium methoxide in an organic solvent such as
(R in the above formula²⁰, R^{twenty one}And X 'have the above significance.
Do).   R²⁰And R^{twenty one}Are the same, the reaction can be performed in one step. Control reaction conditions
The degree of reaction (ie, one of the hydrogen atoms on the methylene group²⁰By
Or replace both with R²⁰Is replaced by).   The compound of formula (IX) has the formula (X): (Where R¹⁶And R¹⁷Has the meaning described above) under conventional conditions.
Strong bases such as umdiisopropylamide and (b) CH_ThreeO_TwoTo react with CCl
Can be manufactured more.   The compound of formula (X) has the formula (XI): And a compound of formula R¹⁶Reacting the compound of X 'in the presence of a base and optionally R^1
7X ′ to react with the compound (R in the above formula¹⁶, R¹⁷And X ′ is the formula (IX)
Has the same significance as described for the reaction of   Alternatively, the compound of formula (IA) can be used in reaction scheme (c). A compound of formula (VIIIA) as described and a compound of formula (XII): (Where R¹Has the above significance) in the presence of aluminum trichloride.
Can be produced by   This type of reaction has been reported by Merenyi and Nilson) (Acta Chem, Sca).
nd, 1963,17, 1801 and Acta Chem. Scand, 1964,68, 1368).   The compound of the formula (XII) is a known compound or is prepared from a known compound by a conventional method.
Can be manufactured.   Furthermore, R¹⁶, R¹⁷, R²⁰And R^{twenty one}Are the same as those of formula (IA): And a compound of formula R¹⁶X ′ compound (R in the above formula¹, R¹⁶And X 'have the above significance
) In the presence of a base.   A suitable base for use in this reaction is a strong base such as sodium methoxide.
is there.   The reaction is suitably carried out in an organic solvent such as methanol at a temperature of 0 to 100 ° C.
It is.   Said compounds of formula (I) are active as herbicides and are therefore another aspect of the present invention.
According to the invention, the compounds of formula (I) described above are added to undesired plants or to the growth medium of said plants.
Seriously damaging undesired plants, consisting of applying an effective amount of
Provides a way to kill this.   The compounds of formula (I) are effective against a wide range of weeds, including monocot and dicot weeds.
It is active. The compound has some selectivity for certain plants, especially corn
Can be indicated.   The compounds of formula (I) may be applied directly to plants (post-emergence application) or germinated in plants.
Can be applied to the previous soil (pre-emergence application).   The compounds of the formula (I) themselves inhibit plant growth or cause significant damage to plants.
Can be used to hurt or kill plants, but may be used as a solid or liquid diluent.
And a carrier comprising the compound of the present invention in admixture with a carrier.
New   Therefore, according to yet another aspect, the present invention provides A plant growth-inhibiting group comprising a compound of the formula (I) and an inert carrier or diluent.
A composition, a composition for damaging a plant or a composition for withering a plant is provided.   The composition containing the compound of formula (I) may be a diluent prepared for immediate use.
There are thickening compositions and concentrated compositions which usually require dilution with water before use.
You. Preferably, the compositions contain from 0.01 to 90% by weight of the active ingredient. Use
Preferably, the dilute composition prepared above contains 0.01 to 2% of the active ingredient.
Concentrated compositions can contain from 20 to 90% of the active ingredient, with 20 to 70% usually being preferred.   Solid compositions are prepared by dividing the active ingredient into finely divided solid diluents such as kaolin and ben.
Tonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia
, Granules or powders mixed with fuller's earth and gypsum. The solid composition also
A dispersible powder or humectant comprising a wetting agent that facilitates dispersion of the powder or granules in a liquid.
Can also be in the form of granules You. The solid composition in powder form can be applied as foliar dust.   Liquid compositions may be a solution or solution of the active ingredient in water, optionally containing a surfactant.
In a water-immiscible organic solvent consisting of a dispersion or dispersed as droplets in water
Or a solution or dispersion of the active ingredient.   The surfactant can be a cationic, anionic or non-ionic agent. Sun
The on-agent is, for example, a quaternary ammonium compound (eg, cetyltrimethyl bromide).
Nmonium). Suitable anionic agents are soaps, sulfuric acid aliphatic monoesters.
Ter salts, such as sodium lauryl sulfate and salts of sulfonated aromatic compounds
Sodium dodecylbenzenesulfonate, sodium lignosulfonate,
Cium and ammonium, butylnaphthalene sulfonate, and diisopropyl-
And a mixture of sodium salts of triisopropyl-naphthalenesulfonic acid.
Suitable non-ionic drugs include oleyl alcohol or cetyl alcohol Condensate product of fatty alcohol and ethylene oxide or octyl phenol
Or alkylphenols such as nonylphenol and octylcresol
It is a condensation product with tylene oxide. Other nonionic drugs include long chain fatty acids and
Partial esters derived from hexitol anhydrides, such as sorbitan monolaurate
, A condensation product of ethylene oxide and the above partial ester, and lecithin.
.   The aqueous solution or dispersion optionally contains one or more wetting or dispersing agents.
Dissolve the active ingredient in water or an organic solvent, then use an organic solvent
Add the resulting mixture to water, optionally containing one or more wetting or dispersing agents
Can be prepared. Suitable organic solvents include, for example, ethylene dichloride,
Isopropyl alcohol, propylene glycol, diacetone alcohol, tol
There are ene, kerosene, methylnaphthalene, xylenes and trichloroethylene
.   Compositions used in the form of aqueous solutions or dispersions may contain active ingredients. The concentrate is generally supplied in the form of a concentrate containing a high proportion of
Diluted in These concentrates are usually required to withstand long-term storage,
Moreover, after such storage, they are diluted with water and applied with a normal spraying device.
Need to be able to form an aqueous solution that remains homogeneous for a sufficient time to
Is done. Concentrates conveniently contain 20-90% by weight of one or more active ingredients
And preferably contains from 20 to 70% by weight of the active ingredient.   One or more diluents may be prepared for use, depending on the intended purpose.
Of the active ingredient in varying amounts; 0.01-10.0% by weight, preferably 0.1-2% by weight
% Of one or more active ingredients is usually used.   Preferred forms of the concentrated compositions are finely divided and include surfactants and suspending agents.
Contains active ingredient dispersed in water in the presence. Suitable suspending agents are hydrocolloids
For example, polyvinylpyrrolidone and sodium carboxymethyl cellulose
, Plant Natural gums such as gum arabic and gum tragacanth. Preferred suspending agents are thixotropic
Agents that also impart properties and increase the viscosity of the concentrate. Preferred suspending agents
Examples include hydrated colloidal inorganic silicates, such as montmorillonite,
, Nontronite, hectorite, sapolite and sauconite. Bentona
Sites are particularly preferred. Other suspending agents include cellulose derivatives and polyvinyl alcohol.
There is.   The rate of application of the compound of the present invention will be, for example, the compound chosen for use, to suppress growth.
Apply the type of plant, formulation and compound chosen to be used for leaf or root absorption.
It depends on a number of factors, including whether to try. However, in general
As an appropriate guide, an application rate of 0.005 to 20 kg per hectare is appropriate.
An application rate of 0.1 to 10 kg per kutar may be preferred.   The compositions of the present invention may comprise, in addition to one or more compounds of the present invention,
But can contain one or more of the compounds not of the invention. You. Thus, according to yet another embodiment, the present invention relates to a method for preparing at least one of the above formulas (I)
A herbicidal composition comprising a mixture of a herbicidal compound and at least one other herbicide;
I do.   Another herbicide can be any herbicide that does not have the above formula (I). Generally special
It is a herbicide that has a complementary effect for certain uses. For example, in some situations, it may be mixed with contact herbicides.
In some cases, it may be desirable to use the compound of the formula (I).   Examples of useful complementary herbicides include:   A. Benzo-2,1,3-thiadiazin-4-one-2,2-dioxide such as 3-isopro
Pyrbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (bentazone);   B. Hormonal herbicides, especially phenoxyalkanoic acids such as 4-chloro-2-methylph
Enoxyacetic acid (MCPA), 2- (2,4-dichlorophenoxy) propionic acid (dichloropro
), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 4- (4-chloro-2-methylph
Enoxy) butyric acid (MCPB), 2,4-dichlorophenoxy vinegar Acid (2,4-D), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), 2- (4-chloro-2-methyl
Rufenoxy) propionic acid (mecoprop) and derivatives thereof (eg, salts,
Stels and amides);   C. 3- [4- (4-halophenoxy) phenyl] -1,1-dialkyl urea such as 3- [4-
(4-chlorophenoxy) phenyl] -1,1-dimethylurea;   D. Dinitrophenols and their derivatives (eg acetate) such as 2-
Methyl-4,6-dinitrophenol (DNOC), 2-t-butyl-4,6-dinitrophenol
(Dinoterb), 2-sec-butyl-4,6-dinitrophenol (dinoceb) and its
Ester of dinoseb acetate;   E. dinitroaniline herbicides such as N, N'-diethyl-2,6-dinitro-4-tri
Fluoromethyl-m-phenylenediamine (dinitramine), 2,6-dinitro-N, N-
Dipropyl-4-trifluoromethylaniline (Trifluralin) and 4-methyls
Ruphonyl-2,6-dinitro-N, N-dipropylaniline (nitralin);   F. Phenylurea herbicides such as N '-(3,4-dichlorophenyl) -N, N-dimethyl
Urea (diuron) and N, N-dimethyl-N '-[3- (trifluoromethyl) phenyl]
Urea (flumetulon);   G. Phenylcarbamoyloxyphenylcarbamate such as 3- [methoxyca
Rubonylamino] phenyl (3-methylphenyl) carbamate (fenmedifa
) And 3- [ethoxycarbonylamino] phenylphenylcarbamate (des
Mejifamu);   H. 2-phenylpyridazin-3-one such as 5-amino-4-chloro-2-phenylpy
Lidazin-3-one (pyrazone);   I. Uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil
Nasyl), 5-bromo-3-sec-butyl-6-methyl-uracil (Bromasil) and 3-
t-butyl-5-chloro-6-methyl-uracil (terbacil);   J. Triazine herbicides such as 2-chloro-4-ethylamino-6- (i-propylamino
) -1,3,5- tria Gin (atrazine), 2-chloro-4,6-di (ethylamino) -1,3,5-triazine (
Simazine) and 2-azido-4- (i-propylamino) -6-methylthio-1,3,5-tria
Gin (adiprotrine);   K. 1-alkoxy-1-alkyl-3-phenylurea herbicides such as 3- (3,4-dichloro
Phenyl) -1-methoxy-1-methylurea (linuron), 3- (4-chlorophenyl)-
1-methoxy-1-methylurea (monolinuron), 3- (4-bromo-4-chloropheni)
Le) -1-methoxy-1-methylurea (chlorbromuron);   L. Thiol carbamate herbicides such as S-propyldipropylthiocarbamate
G (Bernolate)   M. 1,2,4-triazin-5-one herbicide such as 4-amino-4,5-dihydro-3-methyl
6-phenyl-1,2,4-triazin-5-one (metamitron) and 4-amino-6-t-
 Butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one (Metrib
gin);   N. Benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 3,6-dic
Roll-2-methoxybenzoic acid (dicamba) and 3-amino-2,5-dichlorobenzoic acid (
Chloramben)   O. Anilide herbicides such as N-butoxymethyl-chloro-2 ', 6'-diethylacetate
Toanilide (butachlor), corresponding N-methoxy compound (arachlor), corresponding N-
i-propyl compound (propachlor), 3 ', 4'-dichloropropionanilide (
Propanyl) and 2-chloro-N- [pyrazol-1-ylmethyl] aceto-2 ', 6'-
Xylidide (metazachlor);   P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile (dichlorobenzene)
Benyl), 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil) and
3,5-diiodo-4-hydroxybenzonitrile (ioxinyl);   Q. Haloalkane herbicides such as 2,2-dichloropropionic acid (Dalapon),
Lichloroacetic acid (TCA) and salts thereof;   R. diphenyl ether herbicides such as 4-nitrophenyl 2-nitro-4-trifur
Ormethylphenyl ether (fluorodiphen), methyl 5- (2,4-dichlorof)
Enoxy) -2-nitrobenzoate (bifenox), 2-nitro-5- (2-chloro-
4-trifluoromethylphenoxy) benzoic acid (ashifluorfen) and its
Salts and esters, 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nit
Rophenyl ether (oxyfluorphene) and 5- (2-chloro-4- (trifluoro)
Methyl) phenoxy-N- (methylsulfonyl) -2-nitrobenzamide (fomesaf
)); And   S. phenoxyphenoxypropionate herbicide such as 2- [4- (4'-trifur
Ormethyl phenoxy) -phenoxy] -propionic acid methyl ester
-Methyl), 2- {4-[(5-trifluoromethyl) -2- (pyridinyl) oxy]
Phenoxy} propanoic acid (fluazifop) and its ester, 2- {4-[(3-
Lor-5-trifluoromethyl) -2- (pyridinyl) oxy] phenoxy C} propanoic acid (haloxyfop) and its ester, 2- {4-[(6-chloro-2-
Quinoxalinyl) oxy] phenoxy} propanoic acid (xylopof)
Stele; and   T. cyclohexanedione herbicide such as 2,2-dimethyl-4,6-dioxo-5- {1- [
(2-propenyloxy) amino] -butyridine} cyclohexanecarboxylic acid (allo
Ximidine) and salts thereof, 2- (1-ethoxyimino) butyl-5- [2- (ethylthio)-
Propyl] -3-hydroxy-2-cyclohexane-1-one (sethoxydim), 2- [
-(3-chloroallyloxyimino) butyl] -5- (2-ethylthiopropyl) -3-hydrido
Roxycyclohex-2-enone (cloproxydime), 2-[(1-ethoxyimino
) Butyl] -3-hydroxy-5-thian-3-ylcyclohex-2-enone (cyclo
Kishidim); and   U.Sulfonylurea herbicides such as 2-chloro-N- (4-methoxy-6-methyl-1,3,5-
 Triazin-2-yl) -aminocarbonyl) benzenesulfone Amide (chlorosulfuron), methyl 2-{[((4,6-dimethyl-2-pyrimidinyl) amido
ノ) carbonyl] amino} -sulfonylbenzoic acid (sulfomerone), 2-{[(3- (4
-Methoxy-6-methyl-1,3,5-triazin-2-yl) carbonyl) amino] sulfo
Nyl} benzoic acid (methsulfuron) and esters thereof;   V. Imidazolidinone herbicides such as 2- (4,5-dihydro-4-isopropyl-4-me
Cyl-5-oxoimidazole-2-imidazoline-2-yl) quinoline-3-carboxyl
Acid (imazaquin), methyl 6- (4-isopropyl-4-methyl-5-oxo-2-yl)-
m-toluate and p-toluate isomers (AC222293);   W. Arylanilide herbicides such as 1-methylethyl-N-benzoyl-N- (3-chloro
Ru-4-fluorophenyl) -L-alanine (flam-prop-isopropyl), ethi
N-benzoyl-N- (3,4-dichlorophenyl) -DL-alaninate (benzoylpro
-Ethyl), N- (2,4-difluorophenyl) -2- [3- (trifluoromethyl) phenoxy] -3-pyridinecarboxamide (difluo
Phenican); and   X. Amino acid herbicides such as N- (phosphonomethyl) glycine (glyphosate)
And DL-homoalanine-4-yl (methyl) phosphinic acid (phosphinothricin) and
And their salts and esters; and   Y. organic arsenic herbicides such as monosodium methane arsenate (MSMA); and   Z. Various herbicides such as the following herbicides, N, N-dimethyl-diphenylacetoate
Mido (diphenamide), N- (1-naphthyl) phthalamic acid (naptaram) and 3-
Amino-1,2,4-triazole, 2-ethoxy-2,3-dihydro-3,3-dimethylbenzo
Furan methanesulfonate (ethofumesate), 7-oxabicyclo (2,2,1) hep
Tan, 1-methyl-4- (1-methylethyl) -2- (2-methylphenylmethoxy) -exo
(Sinmethylin);   AA. Examples of useful contact herbicides include:   Bipyridylium herbicides, for example, the active moiety is 1,1'-dimethyl-4,4'-dipyridyl
Herbicide (paraquat), which is umium ion, and the active moiety is 1,1'-ethylene-2,2 '
-A herbicide (diquat) which is a dipyridylium ion;   The following examples illustrate the preparation of representative compounds of the present invention.Example 1   This example illustrates the preparation of compound No. 1 in Table I.   2-thiophenecarboxylic acid chloride (1.1) in anhydrous dichloromethane (50 ml).
2 ml), dimedone (1.57 g) and triethylamine (1.7 ml) were added dropwise. Reaction mixture
The mixture was stirred at room temperature for 1.5 hours and then evaporated to dryness to give a soft solid (4.83g).   Add anhydrous acetonitrile (35 ml) to the solid and dissolve it to form a yellow solution
did. Triethylamine (3.2 ml) and acetone cyanohydrin (6 drops) were dissolved in the solution.
Was added to the liquid, which was then stirred at room temperature for 2 hours. Hexane 50: Ethyl acetate 50: Column chromatography using a silica column with an eluent consisting of acetic acid 1
Upon purification, the major orange band was collected and crystallized on standing to give compound No1 (97%
Yield).Example 2   This example illustrates the preparation of compound No. 2 in Table I.   Chloride of 2,5-dichlorothiophenic acid (1.06 g) in anhydrous acetonitrile (25 ml)
) And dimedone (0.70 g) was cooled in a water bath and triethylamine (0.76 ml) was added.
Acetonitrile (5 ml) was added dropwise. The mixture was stirred at room temperature for 0.5 hour,
Add triethylamine (1.4 ml) and acetone cyanohydrin (4 drops) and stir.
Continued for 20 hours, after which the solution was evaporated to dryness.   The residue is dissolved in ethyl acetate and the solution is dissolved in hexane 50: ethyl acetate 50: acetic acid 1: 1.
Applied to a silica column using different eluents and the major orange band was collected and solidified.
I let you.   Recrystallization from hexane and column chromatography as described above Further purification by chromatography afforded compound No. 2 (0.24 g).Example 3   This example illustrates the preparation of compound No. 5 in Table I.   5-bromo-2-thiophenecarboxylic acid (2.09 g), dichloroethane anhydride (30 ml) and
And thionyl chloride (0.75 ml) were heated together at 80 ° C. for 4 hours. This mixture in a water bath
Cool and add dimedone (1.40 g), followed by tris in anhydrous dichloroethane (5 ml).
Liethylamine (2.8 ml) was added dropwise. After 1 hour at room temperature
(2.8 ml) and acetone cyanohydrin (6 drops) were added and stirring continued for 15 hours.
. The solution is then left at room temperature for a total of 3 days, after which it is evaporated to dryness and the residue is
The resulting suspension is dissolved in ethyl acetate, and the resulting suspension is applied to a silica column.
Elute with an eluent consisting of ethyl acetate 50: acetic acid 1 and collect the major orange band.
It solidified to give compound No. 5 as an orange solid (1.26 g). Example 4   This example illustrates the preparation of compound No. 6 in Table I.   5-methyl-2-thiophenecarboxylic acid (0.71 g) and cyclohexane-1,3-dione (0
.5g) and a small amount of (4-dimethylaminopyridine) (100mg) in anhydrous dichloromethane (
20ml) at 15 ° C and dicyclohexylcarbodiimide (1.02g) was added.
The reaction mixture was stirred at 18-20 ° C. for 3-4 hours, then filtered and evaporated. can get
Anhydrous acetonitrile (8 ml), acetone cyanohydrin (4 drops) and
Liethylamine (1.4 ml) was added and the mixture was stirred at room temperature for 2-3 hours, followed by evaporation.
It was allowed to dry.   The residue was purified by column chromatography using hexane 70: ethyl acetate 30: acetic acid 3 as eluent.
Purify by chromatography, collect the major yellow band, evaporate and cream
Compound No. 6 was obtained as a color solid (0.38 g).Example 5   This example illustrates the preparation of compound No10 in Table I.   5-Chloro-2-thienoyl chloride (8.0 g, 44 mmol) and 1,3-cyclohexane
Dione (5.0 g, 44 mmol) was dissolved in 150 ml of methylene chloride. Triethylua
Min (15 ml, 110 mmol) was added and the resulting mixture was stirred at room temperature for 15 minutes. The
The solution was washed with diluted hydrochloric acid, 5% potassium carbonate and saturated sodium chloride, and dried over anhydrous sulfuric acid.
Dried over magnesium and concentrated in vacuo. Residue in 100 ml of acetonitrile
Dissolved. Triethylamine (15 ml, 110 mmol) and acetone cyanohydrin
(0.2 g) was added and the mixture was stirred at room temperature for 2 hours. After dilution with ether
The solution was washed with dilute hydrochloric acid and extracted with 5% potassium carbonate. Acidify the basic extract with hydrochloric acid
And extracted with ether. Washing the ether extract with saturated sodium chloride,
Dry over magnesium sulfate and concentrate in vacuo to 3.8 g of the desired product (m.p. 31
(~ 35%). This is the same as for nuclear magnetic resonance spectroscopy, infrared absorption. It was identified by yield and mass spectroscopy.Example 6   The examples illustrate the preparation of compound No. 42 in Table I.   4-carboxyl-1-methyl-5-trifluoromethyl-1H-pyrazole (5.0 g, 26
(Mole) in a mixture of tetrahydrofuran (25 ml) and acetonitrile (25 ml).
Let it go. Dicyclohexylcarbodiimide (5.3 g, 26 mmol) was added to give
The resulting mixture was stirred at room temperature for 5 minutes. 1,3-cyclohexanedione (2.9 g, 26 mmol
Was dissolved in a mixture of tetrahydrofuran (25 ml) and acetonitrile (25 ml).
This was added to the above mixture and the resulting mixture was allowed to stir at room temperature overnight. Reaction mixture
The mixture was filtered and the filtrate was concentrated in vacuo. Dissolve the residue in acetonitrile (100 ml)
I let it. Triethylamine (9 ml, 66 mmol) and trimethylsilyl cyanide (
0.2 g) and the mixture was stirred at 50 ° C. for 4 hours. After dilution with ether,
Wash the solution with dilute hydrochloric acid and add 5% potassium carbonate. Um. The basic extract was acidified with hydrochloric acid and extracted with ether. Athe
The extract is washed with saturated sodium chloride, dried over anhydrous magnesium sulfate,
Concentration in vacuo gave 2.7 g of the desired product as a yellow solid (m.p. 118-122 ° C.).
Was. It is then identified by nuclear magnetic resonance spectroscopy infrared spectroscopy and mass spectroscopy
Was done.   Compounds Nos. 7-71 and 78 were prepared by a method similar to that used in Example 5 or 6.
Was built.Example 7   This example illustrates the preparation of compound No 79 in Table II.   Step a   Ester (i) (4.17 g) was dissolved in isopropyl alcohol (50 ml) and water (5 ml)
Sodium hydroxide (0.77 g) in the flask was added with stirring. The The mixture was heated under reflux for 2 hours, then poured into 2M aqueous hydrochloric acid to quench the reaction.
It was made. The product is then extracted into ethyl acetate and the extract is dried over magnesium sulfate.
And dried. Concentration under reduced pressure gave acid (ii) as a yellow solid.Step b   2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione (0.50 g) and Step (a)
These acids (0.58 g) were stirred together in anhydrous dichloromethane (DMAP) (approximately 50 mg).
Chlohexylcarbodiimide (0.47 g) was added and the mixture was left at room temperature overnight.
Was. The reaction mixture was filtered and concentrated under reduced pressure to give a yellow solid. This solid is
Dissolved in tonitrile and added triethylamine (0.76 ml). Acetone cyano
Hydrine (4 drops) was added and the mixture was stirred at room temperature for 5 hours. Then this is 2M
And then extracted with ethyl acetate, dried, concentrated under reduced pressure, and ethanol
The compound N was recrystallized from ethanol / ethyl acetate to give a yellow crystalline solid (0.15 g).
o78 was obtained. Example 8   This example illustrates the preparation of compound No. 80 in Table II.Step a   Ethyl 2,4-dimethylthiazole-5-carboxylate (3.0 g, 0.016 mol)
Sodium hydroxide dissolved in isopropyl alcohol (50 ml) and water (5 ml)
(0.718, 0.018 mol) was added. The reaction mixture was stirred at room temperature for 1 hour and then
Heat under flowing water for 1 hour, pour into water, acidify with 2M hydrochloric acid solution and extract with ethyl acetate
did. The aqueous phase is concentrated under reduced pressure, triturated with water, filtered and filtered to a pale pink solid (m.p.
).Step b   2,2,4,4-tetramethylcyclohexane-1,3,5-trione (0.50 g, 2.75 mmol)
Is dissolved in dichloromethane (30 ml), and the product from step (a) is combined with DMAP (about 50 mg).
Dicyclohexylcarbodiimide (0.47 g) was added. Reaction mixture at room temperature for 1 hour
While stirring, then filtered and concentrated under reduced pressure. The residue was dissolved in acetonitrile (30 ml), and triethylamine (0.76 ml) was added to acetone.
Added with cyanohydrin (4 drops). The reaction mixture is stirred at room temperature for 2 hours and then
And heated under reflux for 1.5 hours. Then, the reaction mixture was poured into a 2M aqueous hydrochloric acid solution, and
Extract with ethyl acid, dry and concentrate under reduced pressure to give a yellow oil and solid
, Solid is CH_TwoCl_TwoAnd the triketone raw material was removed. Compound No80 is yellow
Obtained as a colored oil.   Compounds Nos. 72 and 83 were prepared by a method similar to that described in Examples 7 and 8.
I let you.Example 9   This example illustrates the preparation of compound No81 in Table II.Step a   5- (2-pyridine) thiophene-2-carboxylic acid (1.0 g) was added to toluene (50 ml) and
Stir in tilformamide (3 drops). Thionyl chloride (1.6 ml, 9.76 mmol)
Is added and the reaction mixture is stirred at room temperature for 6 hours and then heated under reflux for 1 hour, Filtered. Concentration under reduced pressure gave a yellow solid (1.08 g).Step b   Compound (iii) (0.50 g) and the acid chloride from step (a) (0.63 g) were treated with anhydrous acetonite.
Stirred in ril (15 ml) at room temperature. Triethylamine (0.38 ml) was added and the cloudy yellow
The color suspension turns clear orange as triethylamine is added and then clears
Turned dark yellow. The reaction mixture was then stirred at room temperature for 2 hours.
(0.76 ml) and acetone cyanohydrin (4 drops) were added. Stir at room temperature for 6 hours
Later, the reaction mixture was poured into water (50 ml), acidified with 2M HCl (100 ml) and ethyl acetate (1 ml).
00 ml), the ethyl acetate phase is washed with 50% sodium carbonate solution (100 ml),
The basic phase was then acidified with 2M HCl. The mixture is then extracted with dichloromethane.
The dichloromethane phase was washed with brine (25 ml) and dried over MgSO_FourDried on, filtered,
Concentration under reduced pressure gave a light yellow solid.   Compound No 81 was separated using a 75: 175: 1 ethyl acetate / hexane / acetic acid solvent system.
Obtained by preparative plate chromatography. A yellow oil that crystallizes when left untreated
Obtained.   Compounds Nos. 73, 74, 75 and 76 were prepared by a method similar to that described in Example 9.
Was.Example 10   This example illustrates the preparation of compound No77.  The salt (V) (0.84 g) was treated with toluene (35 ml) and DMF (5 drops) was added dropwise. Stirred suspension
The suspension was treated dropwise with oxalyl chloride (0.75 ml). With this addition, the color only changes to purple
Uneven foaming occurred. The mixture was stirred overnight at room temperature and then evaporated under reduced pressure
An off-white solid was obtained. This was treated with acetonitrile (15 ml) and partially dissolved.
I let you. The mixture The mixture was stirred while cooling in an ice bath, and cyclohexane-1,3-dione (0.6 g) was added.
Then triethylamine (0.75 ml) was added dropwise. Most of the precipitate dissolved. The mixture
The mixture was stirred for 3 hours while maintaining the cooling. Then acetone cyanohydrin (6
Drop) and triethylamine (1.8 ml) was added slowly.   The mixture was then stirred at room temperature for 4 hours and then allowed to stand over the weekend. Light yellow melting
A liquid was obtained. This was filtered and the filtrate was poured into water (100 ml). The resulting alkali
The neutral solution became cloudy when oxidized with dilute HCl.   The mixture was extracted with dichloromethane to give a yellow organic phase. This is sodium carbonate
The aqueous phase was acidified with dilute hydrochloric acid. The resulting cloudy mixture is
Extract with water, the organic phase is washed with water, dried over magnesium sulfate and then dried.
And evaporated to give a yellow oil which hardens on standing to a yellow solid (0.5 g).
As a result, compound No77 was obtained. Biological data   As described above, the compounds described in the present specification produced in the manner described above can be used in various plants.
It is a useful and valuable toxic compound for controlling pests. Selected compounds of the invention
The herbicide was tested as follows.Weeding test before germination   The day before the treatment, seven different weed seeds were applied in a row across the width of a flat box.
One individual plant was used to sow the loamy sand as individual rows. The seeds used
Enokorogosa (FT) (Setaria viridis), Dog millet (WG) (Echinochloa crusgalli),
Wild oats (WO) (Avena fatua), Morning glory (AMG) (Ipomoea lacunosa), Abtilon
  Theoblast (Velvetleaf: VL) (Abutilon theophrasti), Brassica Junce
A (Indian mustard: MD) (Brassica juncea) And Cyperus esculentas (Yel
low nutsedge: YNG) (Cyperus esculentus). After germination depending on the size of the weed
Sowed with enough seeds to give about 20 to 40 seedlings per row.   Using an analytical balance, weigh 600 mg of the test compound onto a piece of glassine weighing paper.
Was. Place the weighing paper and the test compound in a 60 ml wide-mouth transparent bottle, and add 45 ml of acetone or
Dissolved in the substitute solvent. Transfer 18 ml of this solution to a 60 ml wide-mouth clear bottle and
22 ml of water containing polyoxyethylene sorbitan monolaurate emulsifier and
Dilution with an acetone mixture (19: 1) gave a final solution of 0.5% v / v. Then
Of the linear solution calculated to supply 80 gallons per acre (748 L / ha)
It was sprayed on a seed flat box by a spray table. Application rate is 4 lbs / acre (4.48k
g / ha).   After treatment, flat boxes were placed in a greenhouse at a temperature of 70-80 ° F and watered by watering. place
Two weeks after treatment, the degree of damage, ie, the degree of control, was compared with that of untreated control plants of the same age.
Was measured by comparison. 0-100% damage rate control rate for each plant (%)
Where 0% represents no damage and 100% represents complete control.Post-emergence test   Obtain post-emergence results using a similar method except that the test compound is applied to the seedling plants.
Was.   The test results are shown in Tables III and IV below.   Compounds 13, 15, 24, 25, 26, 27, 28, 34, 39 are pregerminated against test plants at given application rates
No activity was shown. Testing at temperature for herbicidal activity   With an equivalent volume of 1000 l per hectare and an application rate of 10 kg per hectare
At the corresponding concentration, the test compound is transferred to the next plant preparation using a mobile boom track sprayer.
Tas (Lt), tomato (To), wild oat (Avena fatua) (Av) and Enokorogosa (Se
taria viridis) (St). Evaluation starts 17-20 days after direct spraying on seeds
Pre-bud activity During which time the seeds were covered with compost. Evaluation also spurts seedling plants
Thirteen days after fog, post-emergence activity was also determined.   The rating scale used was as follows:   0 = 0-25% plant damage   1 = 26-50% plant damage   2 = 51-75% plant damage   3 = 76-100% plant damage   The results of this test are shown in Table V below.   Herbicidal activity against another plant by the compounds of the present invention was tested as follows;   Each compound at a specific concentration is a 4% emulsion of methylcyclohexanone and 3.6 parts
And a one part span 80 blend of 0.4%. Tween 20 is 20 moles
Of surfactants consisting of condensates of ethylene oxide and sorbitan laurate
It is the title. Span 80 is a trade name for a surfactant consisting of sorbitan monolaurate
It is. The drug product must be prepared by dissolving the test compound in the required amount of solvent / surfactant mixture.
Performed by If necessary, add glass spheres and adjust the total volume of the liquid to 5 ml with water.
The mixture was shaken to effect complete dissolution of the compound. Made in this way
The agent, after removal of the glass spheres if necessary, is then brought to a final spray volume (45 m
l).   The spray composition thus produced has a low application rate of 1000 l / ha.
Potted plants were sprayed (post-emergence test). Damage to plants on a scale of 0-5
Spray compared to untreated plants 13 days after evaluation, where 0 is 0-10% plant damage, 1 is 11-25% damage, 2
Is 26-50% damage, 3 is 51-80% damage, 4 is 81-95 damage, 5 is 96-100% damage
Damage.   In a test performed to assess pre-emergence herbicidal activity, test plant seeds were composted.
Sprayed on the surface of a plastic dish plate at an application rate of 1000 l / ha.
The mist composition was sprayed. The seeds were then covered with another amount of compost. 20 after spraying
After day, compare seedlings in sprayed plastic dish to seedlings in unsprayed control dish
The damage was evaluated on the same scale of 0-5.   The test results are given in Table VI below.

Claims (1)

[Claims]   1. Formula (I):Wherein X is oxygen or sulfur; Is the formula: (Where R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is a hydrogen or methyl group)
R; R¹Means up to 10 ring atoms (up to 3 of these ring atoms are selected from oxygen, nitrogen and sulfur)
A mono- or fused bicycloheterocycle containing
The ring is oxo, mercapto, halo, nitro, cyano, amino, mono or dialky
Ruamino, amide, C₁−C₆Alkyl, C_Two−C₆Alkenyl, C_Two−C₆Alkynyl, Si
Chloroalkyl, haloalkyl, haloalkoxy, aryl (fluorine, chlorine, bromine,
C₁−C₆Alkyl or C₁−C₆Optionally substituted with alkoxy), hydroxy, Alkoxy, alkoxycarbonyl, alkylcarbonyl, mono- or dialkyi
Rucarbamoyl, alkylthio, alkylsulfinyl, alkylsulfonyl,
Sulfonamide, alkylcarbonyloxy, alkylcarbonylamino, pyri
Substituted by one or more groups selected from the group consisting of a jyl or thienyl group
Provided that when X is oxygen, R¹Is pyridyl, pyrimidinyl or
IsHeterocycle having two oxygen atoms linked to a benzene ringNot the same)
Represented substituted cyclic dione compound or a salt thereof, enamine or an analog thereof, acylate
G, sulfonate, carbamate or ether derivatives.   2. R¹Is a group of the formula: (Where R^FiveIs hydrogen, C₁−C_FourAlkyl group or halogen, lower alkyl group or lower
An aryl group optionally substituted with a alkoxy group,⁶, R⁷And R⁸Are
(1) hydrogen; (2) halogen; (3) C₁−C_FourAlkyl group; (4) haloalkoxy group; (5) C₁−C_FourA
(6) cyano group; (7) nitro group; (8) C₁−C_FourHaloalkyl group; (9) R⁹SO_n- (Wherein n is an integer of 0, 1 or 2;⁹Is   (a) C₁−C_FourAlkyl group;   (b) halogen, cyano group, C₁−C_TwoAlkoxy group or C₁−C_TwoSubstitute with alkylthio
Done C₁−C_FourAlkyl group;   (c) a phenyl group; or   (d) benzyl group ); (10) -NR^TenR¹¹(Where R^TenAnd R¹¹Is hydrogen or C₁−C_FourAlkyl
(11) R¹²C (O)-(wherein, R¹²Is C₁−C_FourAlkyl group or C₁−C_FourAlkoxy group
(12) -SO_TwoNR^TenR¹¹(Where R^TenAnd R¹¹Has the above significance); or (13)
-N (R^Ten) C (O) R¹¹(Where R^TenAnd R¹¹Has the meaning described above);
The compound of claim 1, wherein   3. R¹Is the formula: (Where R^FiveAnd R⁶Is a group having the meaning of claim 2).
Compound.   4. R¹Is the formula: (Where R⁶, R⁷And R⁸Has the meaning of claim 2;¹²And R¹³One is = N-
And the other is C (R¹⁴) And R¹⁴Is hydrogen, halogen, C₁−C_FourAlkyl group, OCF_Three, C
₁−C_FourAlkoxy group, cyano group, nitro group, C₁−C_FourHaloalkyl group or R¹⁵SO_m(
Wherein m is an integer of 0, 1 or 2;¹⁵Is C₁−C_FourWhich is an alkyl group).
The compound according to claim 1, which is a group of the formula:   5. R¹Is the formula:Wherein Z contains up to three heteroatoms selected from oxygen, sulfur and nitrogen;
A 5- or 6-membered saturated or unsaturated condensed ring).
Stuff.   6. R¹Is furyl, thienyl, pyrrolyl, pyrazolyl, pyridyl, pyrimidinyl
, Imidazolyl, thiazolyl, dithiol, oxathiol, oxazolyl, i
Soxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiodiazo
Ryl, oxatriazolyl, dioxazolyl, oxathiazolyl, oxathiol
, Dioxinyl, pyridazinyl, pyrazinyl, piperazinyl, pyrazinyl
Oxazinyl, isoxazinyl, oxathiazinyl, morpholinyl, azepinyl
, Oxepinyl, Thiepinyl, Diazepinyl, Benzofuranyl, Isobenzofuran
Nil, benzothienyl, isobenzothienyl, thionaphthalenyl, isothionaph
Tarenyl, indolyl, isoindolyl, indazolyl, indoleninyl, iso
Benzazolyl, pyranopyrrolyl, isoindazolyl, indoxazinyl, benzo
Xazinyl, benzopyranyl, quininyl, isoquininyl, sinolinyl, lid
Radinyl, quinoxalinyl, quinazolinyl, naphthyridinyl, pyridopyridinyl
, Pyranyl, thiopyranyl, chromenil, thiachromenyl, benzoxazolini
The compound according to claim 1, which is a benzoisoxazolinyl or purine group.   7. 2. The compound according to claim 1, wherein X is oxygen.   8. Formula IA:(Where R^{twenty five}Is R in claim 1¹Is the same as defined for¹⁶, R¹⁷, R²⁰
And R^{twenty one}Is the same as defined in claim 1, except that at least R¹⁶And R¹⁷ Or R²⁰And R^{twenty one}Wherein both are not hydrogen).
A compound or a salt thereof, an acylate or a sulfonate derivative.   9. R¹⁶, R¹⁷, R²⁰And R^{twenty one}Is a methyl group.   10. Formula (II): (Where R¹, X, X^TwoAnd Y are as defined for formula (I))
Transfer in the presence of a cyanide source and a mild solvent.
A method for producing the compound of the formula (I) according to claim 1.   11. Formula (VIIIA): (Where R¹⁶, R¹⁷, R²⁰And R^{twenty one}Has the meaning of claim 1);
Formula (XII): (Where R¹Has the meaning of claim 1) and aluminum trichloride
The reaction of the compound of formula (IA) according to claim 8, characterized in that the reaction is carried out in the presence of
Construction method.   12. Formula (XIII): (Where R¹Has the meaning given above) and a compound of formula R¹⁶X¹(Where R¹⁶Means the above
Justice, X¹Is a leaving group) in the presence of a base.
Characteristic, R¹⁶, R¹⁷, R²⁰And R^{twenty one}The formula (IA) according to claim 8, wherein are the same.
Manufacturing method of compound.   13. A herbicide set comprising the compound of formula (I) according to claim 1 and a carrier or diluent.
Adult.