JPS6157568A - Cyclohexenone derivative, manufacture and herbicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to cyclohexenone derivatives, a process for their preparation, and herbicides containing 1 to "C" of said compounds as an active substance.

PRIOR ART It is known to use cyclohexenone derivatives in broad-leaved plant cultivation to control undesirable carnivores (German Patent Application No. 24 391).
04 Specification). Furthermore, derivatives substituted with 7-chloroalkenyl in the 5-position are known from DE 30 32 973 A, which are likewise effective as herbicides at °C.

Problems to be Solved by the Invention The object of the present invention was to provide new compounds that are effective as herbicides.

Means for Solving the Problem By the way, the formula I: [wherein A is one or two oxirane or thiirane rings fused together]7. , a cycloalkyl group having from 5 to 12 ring members and substituted by up to 4 methyl groups (and also bridged by an alkylene chain having up to 3 carbon atoms) , R1 represents a hydrogen atom, a methoxycarbonyl group or a cyano group, R2 represents an alkyl group having 1 to 4 carbon atoms, and R3 represents an alkyl group having 1 to 3 carbon atoms, 3 or a halogen alkyl group or propargyl group having 4 carbon atoms and 1 to 3 halogen atoms] and salts thereof are particularly effective in killing weeds against plants belonging to the family Hematinaceae. It has been found that these substances have temperature selectivity in broad-leaved plants as well as monocotyledonous plants that do not belong to the family Helmetaceae.

Compounds of formula I can be produced in a wide variety of forms, all of which are encompassed by the following claims: Cycloalkyl groups having 5 to 12 ring members and optionally substituted by up to 4 methyl groups and bridged by an alkylene chain with up to 3 carbon atoms, e.g. epoxycyclopentyl , epoxycyclohexyl, epoxycyclopentyl, epoxycyclooctyl, epoxycyclododecyl, jepoxycyclododecyl, epoxymethylcyclopentyl, dimethylepoxycyclopentyl, epoxymethylcyclohexyl, dimethylepoxycyclohexyl, epoxytrimethylcyclohexyl, epoxytetramethylcyclohexyl, epoxybicycloheptyl, Represents poxytrimethylcyclohexyl, epoxydimethylbicycloheptyl, shrimpthiocyclopentyl, shrimpthiocyclohexyl, shrimpthiobicycloheptyl t3
．． Particular preference is given to the 4-epoxycyclobentel group.

R2 in formula 1 is a straight-chain or branched alkyl group having 1 to 4, preferably 2 or 3 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n
-Butyl, B-butyl, 1-butyl, t-butyl.

The group represented by R3 in formula 1 may be propargyl, alkyl having 1 to 3 carbon atoms, alkenyl having 3 or 4 carbon atoms, or containing up to 3 halogen atoms. halogenalkenyl groups having 3 or 4 carbon atoms, such as methyl, ethyl, n-propyl,
l-propyl, n-butyl, 1-butyl, L-butyl,
t-butyl, allyl, 3-chloroprop-2-enyl,
2-chloro-prop-2-enyl, i,3-dichloro-
Prop-2-enyl, 2,3.3-)lichloropro7
-2-enyl.

Salts of compounds of formula I or agriculturally usable salts, such as alkali metal salts, especially potassium or sodium salts,
Alkaline earth metal salts are suitable, especially calcium, magnesium or barium salts, manganese-1-copper-1-zinc or iron salts, and also ammonium, sulfonium and phosphonium salts.

The compound of formula l is a tricarbonyl compound represented by the formula ■: [wherein A, R1 and R2 are the above-mentioned ones]; Y represents an anion] by reacting with a hydroxylamine conductor.

The reaction is advantageously carried out in a heterogeneous phase in an inert diluent at a temperature of 0 DEG to 80 DEG C. or between 0 DEG C. and the boiling point of the reaction mixture in the presence of a base. Suitable bases are, for example, carbonates, bicarbonates, acetates, alcoholades, hydroxides or oxides of alkali metals or alkaline earth metals, in particular sodium, potassium, magnesium, calcium. Additionally, organic bases such as pyridine or tertiary amines can also be used.

Diluents include, for example, dimethyl sulfoxide, alcohols such as methanol, ethanol, impropatol, benzene, optionally chlorinated hydrocarbons such as chloroform, dichloroethane, hexane, cyclohexane, esters such as ethyl acetate, cyclic ethers such as dioxane, Tetrahydrofuran is suitable.

Mixtures of these diluents can also be used.

The reaction is complete after a few hours and the reaction product can then be isolated by concentrating the mixture, adding water and extracting with a non-polar solvent such as methylene chloride and evaporating the solvent under reduced pressure. .

Further, the compound of formula l is a compound of formula
A hydroxylamine represented by NH snow (wherein R1 represents the above) is reacted in an inert diluent at a temperature between 0°C and the boiling point of the reaction mixture, in particular from 15 to 70°C. This can be obtained by Optionally, hydroxylamine can be used in aqueous solution.

Suitable diluents for this reaction are, for example, alcohols such as methanol, ethanol, isopropanol, cyclohexanol, optionally chlorinated hydrocarbons such as hexane, cyclohexane, 1/N, toluene, dichloroethane, esters such as ethyl acetate, nitrites such as acetonitrile, cyclic ethers such as dihydrofuran.

Alkali metal salts of compounds of formula I can be obtained in aqueous solution with sodium hydroxide or potassium hydroxide or in organic solvents such as methanol, ethanol, acetone. It is also possible to utilize sodium and potassium alcoholades as bases.

Other metal salts, such as manganese salts, copper salts, zinc salts, iron salts, calcium salts, magnesium salts and barium salts,
It can be produced by reacting the sodium salt with the corresponding metal chloride in an aqueous solution. Ammonium, sulfonium and phosphonium salts can be prepared with ammonium, -sulfonium or -phosphonium hydroxide compounds of formula I, optionally in aqueous solution.

The tricarbonyl compound of formula (1) is a new substance.

These are cyclohexay-1,3-diones of the formula ■ (which can also exist in the tautomeric form ■1 and the abbreviation) Needs (T@trah@dron L@tt@rs)
, 29, 2491 (1975)).

The new compound of formula (1) is optionally produced as an isomer mixture when reacting the compound (2) and is an imidazole-
or converted in the presence of a pyridine conductor (%
-6305)) It is also possible to produce the enol ester via an intermediate step.

As is clear from the foregoing, tricarbonyl compounds of formula (1) are valuable intermediates for the preparation of herbicide-effective cyclohexenone crocodile conductors of formula (1).

Compound 2 can be obtained according to methods known from the literature, as is clear from the following reaction scheme: A -CHO General formula: The aldehyde of A-CHO can be obtained from the corresponding unsaturated aldehyde by methods known from the literature. method, in which case it may be necessary to protect the aldehyde function.

The silane fibers are reacted in a manner known per se with the corresponding unsaturated aldehydes or aldehyde derivatives and peroxy compounds, such as hydrogen peroxide, -1-butyl hydroperoxide, performic acid, m-chloroperbenzoic acid, or atmospheric oxygen. This can be obtained by

The epoxide structure can also be synthesized from 1,2-norogen hydride by separating hydrogen halide at °C.

Thiirane compounds are described, for example, in "Journal of Chemical Research (J, Ch@rn, Sac,)
1946, p. 1050, from the corresponding epoxy compounds and thiocyanates or thioureas, or from Chem.
s -roayalic compounds) No. 42
Vol., page 340, they can be prepared from the corresponding unsaturated derivatives by reaction with sulfur rearrangement reagents, such as arylthiosulfenyl chlorides.

The conversion process can optionally be carried out in any synthetic step.

EXAMPLE Next, the method for producing the cyclohexenone derivative of formula (2) will be explained with reference to examples. In the examples, parts by weight and parts by volume have a relationship of kp and t.

II (-NMR spectra were detected in deuterochloroform as solvent with tetramethylsilane as internal standard. shows.

3 = single line, d = double line, t = triplet, q = quartet, m =
Multiple lines (strongest signal) Example 1 3.5 parts by weight of 2-butyryl-5-(3,4-epoxycyclohexyl)-cyclohexane-1,3-dione, 1.5 parts by weight of allyl ammonium chloride, and sodium hydrogen carbonate. 1.2 parts by weight was stirred in 50 parts by volume of methanol at room temperature for 16 hours. The solvent was distilled off under reduced pressure, the residue was stirred with water and 50 parts by volume of dichloromethane, the organic phase was separated, the aqueous phase was extracted with 50 parts by volume of dichloromethane, and the combined organic phases were extracted with sulfuric acid. The solution was dried over an IJ column and the solvent was distilled off under reduced pressure. 2-(1-allyloxyimino-butyl)-5-(3,4-epoxycyclohexyl)-3-hydroxy-cyclohex-2-ene-1-
On (effective substance Al) was obtained.

IH-NMR spectrum: = 0.95 (su, 2-9(q), 5.3(m)) Example 2 2-butyryl-5-(3,4-eboxy-dicyclohexylgo-cyclohexane-tt3-dione 3. 5 parts by weight and 0.8 parts by weight of ethoxyamine were stirred in 100 parts by volume of methanol at room temperature for 16 hours. The I solvent was distilled off under reduced pressure, the residue was dissolved in dichloromethane, and the solution was diluted with 5 parts by weight.
It was washed with % hydrochloric acid and water, dried over sulfuric acid and the solvent was distilled off under reduced pressure. 2-(l-Ethoxyimino-butyl)-5-(3,4-epoxycyclohexyl)-3-hydroxy-cyclohex-2-en-
1-one (active substance A2-one).

IH-NMR spectrum = 1.3 (z), 3-2 h), 4.1 (d) Example 3 2-(l-propoxyimino-butyl)-5-(cyclohex-3-enyl)-3- 9 parts by weight of human sexy cyclohex-2-en-1-one and 100 parts by weight of dichloromethane
10 parts by weight of dichloromethane dissolved at 5 to 10°C.
m-chloroperbenzoic acid (approximately 80%) in 0 parts by volume 5.8
parts by weight were added dropwise. After 1 hour, the reaction progress was examined using thin layer chromatography (DCC ready-made Fusilica gel 60 developer cyclohexane/ethyl acetate 1:
l). In addition, if a starting material is present, still another m-
Chloroperbenzoic acid is added dropwise to ensure complete reaction. Excess peracid was removed by shaking with sodium thiosulfate solution. It was further extracted twice with half-saturated sodium bicarbonate solution and once with water, the organic phase was dried over an IJ cum and the solvent was distilled off under reduced pressure. 2- (1-propoxyimino-2-butyl)-
5-(3,4-epoxycyclohexyl)-3-hydroxy-cyclohex-2-en-1-one (active substance A
3) was obtained.

ltt-NMR spectrum = 2.2), 3.1-14. υω In the same manner as in the above example, the following compound was obtained -I! 1
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('Q's -'s -'s sound)
− Prisoner υ! ! LO RI V> RI RI dumb dumb punishment lo lo Q lo C agony flash - flash flash flash flash agony flash flash flash flash agony flash cyclohexenone derivative of heki formula ■ can be used, for example, as a directly sprayable solution, powder, Spraying, misting, dusting, spreading in the form of suspensions, as well as highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oily dispersions, pastes, dusts, dusting agents or granules. Or it can be applied by injection method.

The form of application depends entirely on the intended use; in each case it should be ensured that the active substance of the invention is as finely divided as possible.

For the production of directly splashable solutions, emulsions, pastes or oil dispersions, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, as well as coulter oil, as well as vegetable or animal products, can be used. source oils, aliphatic, cyclic and aromatic hydrocarbons such as penzole, doluol, quidyol, paraffin, tetrahydronaphthalene, alkyl-substituted naphthalene or derivatives thereof such as methanol, ethanol, propatool, phthanol, chloroform, carbon tetrachloride, 7 strong aa solvents such as clohexanol, cyclohexanone, chlorbenzole, isothuolone, etc.
-dimethylformamide, dimethyl sulfoxide,
N-methylpyrrolidone and water are used. Aqueous use forms can be prepared from emulsions, pastes or wettable powders (spray powders), oil dispersions by addition of water. To produce emulsions, pastes or oil dispersions, the substances can be mixed homogeneously in water with wetting agents, adhesives, dispersants or emulsifiers, either as such or dissolved in oil or solvents. . In addition, it is also possible to prepare concentrates of active substance, wetting agents, adhesives, dispersants or emulsifiers and, if appropriate, solvents or oils, which are suitable for dilution with water.

Surface-active substances include: likunin sulfonic acid, naphthalene sulfonic acid, alkali salts of phenolsulfonic acid, alkaline earth salts, ammonium salts, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates. alkaline salts and alkaline earth salts of dibutylnaphthalene sulfonic acid, lauryl ether sulfate, fatty alcohol sulfate, fatty acid alkali salts and alkaline earth salts, sulfated hexadecahalide-11 heptadecanol, octadeca salts of sulfated fatty alcohol glycol ethers, sulfonated naphthalene or condensation products of Natsuta 1) 7m conductor and formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with 7 enol and formaldehyde, poly Oxyethylene-octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol, intridecyl alcohol/', fatty flucol ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acecool, sorbitol ester, likunin,
Sulfite waste liquid and methyl cellulose.

Powders, dusting powders and sprinkles can be prepared by mixing or milling together the active substance and a solid carrier material.

Granules, such as coatings and homogeneous granules, can be produced by binding the active substance to a solid carrier material. Solid carrier materials are, for example, minerals such as silica gel, silicic acid, silicate gel, silicates, talc, carrion, atakure, limestone, chalk, chalk, agglomerate, calcareous yellow clay,
Clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide 1, ground synthetic resins, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as flour, bark, wood and walnut flour, cellulose. powders and other solid carrier materials.

Examples of formulations are as follows.

When 1.90 parts by weight of the compound is mixed with 710 parts by weight of N-methyl-α-pyrrolide, it forms very small droplets.
A solution suitable for use is obtained.

If, 20 parts by weight of compound 2, Kijirol 80'X
8 to 10 moles of ethylene oxide to oleic acid
Appendix 2111 added to 1 mol of N-monoethanolamide
1 part by weight of the product, 5 parts by weight of the calcium salt of dodecylpenzole sulfonic acid and 40 mol of ethylene oxide in 1 mol of castor oil are dissolved in a mixture consisting of 5 parts by weight of the coproduct. By pouring this solution into 100,000 parts by weight of water and finely distributing it, the active ingredients o, oz.
An aqueous dispersion containing x:is is obtained.

■, 20 parts by weight of compound l, 40 parts by weight of cyclohexanone, 30 parts by weight of inbutanol, 7 parts by weight of ethylene oxide
20 moles of addition product added to 1 mole of isooctylphenol! part and 40 moles of ethylene oxide are dissolved in a mixture consisting of 10 parts by weight of the addition product of 1 mole of castor oil. By pouring this solution into 1 part by weight of water and finely distributing it, an aqueous dispersion containing 0.02'M of the active ingredient is obtained.

■, 20 parts by weight of compound 4, cyclohexanol 25
parts by weight, 65 parts by weight of a mineral oil fraction with a boiling point of 21 υ to 280° C. and 40 mol of ethylene oxide are dissolved in a mixture consisting of 10 parts by weight of an adduct of x mol of castor oil. By pouring this solution into 100,000 parts by weight of water and finely distributing it, an aqueous dispersion containing 0.02 parts by weight of the active ingredient is obtained.

v, 20 parts by weight of Compound 6, 3 parts by weight of sodium salt of diisobutyl-naphthalene-α-sulfonic acid, 17 parts by weight of IJ cum salt, and 60 parts by weight of powdered silicic acid gel. and milled in a hammer mill at 0°C. By finely distributing 20,000 parts by weight of water into this mixture, 0 active ingredients can be obtained.
．． A spray liquid containing 1 wt.

M, 3 parts by weight of compound 13, finely granulated kaolin 97
Mix intimately with parts by weight. A propellant containing 3-wt. of active substance is thus obtained.

■30 parts by weight of compound 11 were added to powdered silicic acid gel 92.
parts by weight and 8 parts by weight of paraffin oil which is blown onto the other side of the silicic acid gel. A formulation of active substance with good adhesive properties is thus obtained.

1.20 parts by weight of the compound I were mixed with 2 parts by weight of the calcium salt of dodecylpenzole sulfonic acid and 8 parts of 1kIH+, 7x norsulfonic acid-urea-formaldehyde condensate in fatty alcohol polyglycol ether.
Mix intimately with 221 parts by weight of Jum salt and 68 parts by weight of paraffinic mineral oil. A stable oily dispersion is obtained.

Active application can be carried out by pre-emergence or post-emergence treatment methods. If the active substance has low compatibility with certain cultivated plants (if the herbicide is applied with a sprayer, it should be applied as little as possible to the leaves of sensitive cultivated plants, and the active substance grown under Spraying techniques can also be applied to reach the foliage of undesirable plants or exposed soil surfaces.
post-directed
), tay-by @].

The amount of active substance used is based on the respective season, target plant and growth stage - CU, L125-3 kVha,
Advantageously between 0.05 and Q, 5 kfha.

The effect of the fuchlorohexenone rust conductor of formula I on plant growth is demonstrated in greenhouse experiments. - As cultivation containers, plastic flowerpots with a volume of * 300 cI/l and containing loam sand with about 3.0% humus as subsoil were used. Seeds of test plants were separated by type and sown shallowly. In the pre-emergence treatment method, the active substance is sprayed onto the soil surface immediately after sowing. In this case, the active substance is suspended or emulsified in water as a dispensing agent and is
Sprayed. The amount used was 3°Q kj)/ha.

After application of the chemicals, the containers were lightly watered to promote germination and growth. The container was then covered with a clear plastic hood until the plants grew. This cover ensured uniform germination of the test plants, as long as they were not damaged by the active substance.

For the post-emergence treatment method, the test plants were cared for to a growth height of 3 to 15 (up to) depending on the respective growth form and then treated. Soybeans were planted in peat-enriched cultivation soil. For the post-emergence treatment method, plants either sown directly and grown in the same container were selected, or those that were first planted as seedlings at different degrees Celsius and transplanted into experimental containers a few days before treatment were employed. The amount used for post-emergence treatment varied from 0.06 to 0.125 kVha of active substance. No covering was used in the post-emergence treatment method.

The experimental container was placed in a greenhouse, and the temperature range was set at 20-35°C for varieties that prefer high temperatures, and 10-25°C for varieties that prefer moderate climates.The experimental period was During this period, the plants were cared for and their responses to individual treatments were evaluated.
-100 scale. In this case, lυ0 means that the plant will not germinate or at least the above-ground part will die completely.

The plants used in the greenhouse experiment consisted of the following species: A1op@eurus myosu
roides), oat (Avsna fatua)
), oat (Avsna 5atlvsu), crabgrass (Digitalla singuinallm), golden millet (Eehlnoahloa arus-gall)
i), Dice (Glyelna max), Mouse wheat (Lolium multlflorum)
, Sataria 1tallca, Sinapla alba, Sorghum hal@pense,
Sorghum blcolor, corn (Zea mays).

As a comparative substance, the patent application publication number 3 of the Federal Republic of Germany
2- which is a compound known from [)32973 specification.
(1-allyloxyamino-n-butyl)-5-(cyclohex-1-en-4-yl)-3-hydroxy-cyclohex-2-en-7-1-one (A and 2-(1-
Ethoxyimino-n-butyl)-5-(cyclohexy-
1-en-4-yl)-3-hydroxy-Schiff-tetrahex-2-en-1-one (B) and the compound 2-(l-ethoxy amino-n-butyl)-5-
(Cyclooct-1-en-5-yl)-3-hydroxy-cyclohex-2-eny-1-one (C) and herbicides containing these compounds were used.

In the pre-germination treatment method, for example, compounds 4.6.11 and 1
No. 3 was effective as a herbicide against plants belonging to the family Helicoptaceae, and remained completely harmless against white mustard, a representative of gas cotyledonous plants.

Furthermore, compounds A4 and 6, for example, can be used in a post-emergence treatment method to reduce the amount of active substance 0. When L25vha was used, it showed strong herbicidal activity against a wide spectrum of weeds.

Dicotyledonous plants and dies at °C were not harmed at all.

For example, compounds A 26 , 28 , 5). Although 53, 55 and 61 were used to sufficiently control undesirable weeds, they were completely harmless to the gum leaf plant Kumago palm (an example of a cultivated plant).

Compound No. 8, chosen as an example, was already suitable for controlling undesirable grasshoppers even in small amounts and had excellent compatibility with wheat.

Using the compounds 41 and 2 selected as examples, it is possible to have complete compatibility with soybeans and at the same time to control the problem glass significantly better than with the known comparison substances Contains and B.

Compared to known substance C, for example, the level of herbicidal activity of Compound Mu50 is clearly high, and its suitability for alfalfa is not affected.

Taking into account weed control, compatibility with cultivated plants or a harmless effect on their growth, and because of the variety of applications, the compounds according to the invention can be used in a large number of cultivated plants. For example, the following cultivated plants fall into this category: Onions (Allum espa), Pine nuts (Annums comoaus), Bean beans (Araahls hypoga@a), Asparagus (Asparagus officialnalls)
Oat (Av@na aatlva) Chard (
Beta vulgaria spp, altlsa
ima Satokujisha (B@ta vulgars)
spp, rapa) red sugar beet (Beta vulg)
arls spp, eIIeulenta) Brassie force
s) Brush force Napasu (variety Nabopraseeka) (Br
aasica napus vΔr, napobr
Mouth 8icm) Brush force Napus (variant Opa) (Brasaica napus v&r, rapa)
Braa Power Napas (Weird M Full Pestris 2 (Braa)
aLca apus w&r, ailv@5tri Cam@1lla sin@ns1m Safflower (Carthamua tlnctorlum) Caryi 1llinoinsnsi CiLrua ll mon) Grapefruit (
Citrus rnax1mandaidai (C1tru
s r*tieulata) Naramikan (C1trus)
alnen@i@) Coffee Tsuki (Coffea a
rablea (Coffeacanspori,
Coff@a 1lbsriaa)) Amymelon (Cu
aumLs mela no cucumber (Cueumls 5
ativus) Cynadon daa
tylon) Carrot (Dauaus aarota)
Aprayami (E1a@is guinssni) Strawberry (Fragarla vesea) Soybean (Glycin)
e max) Cotton (Gossypium hirsutum (Goa
aypiumo, arborsum, Gossyp
lum herbaasum.

Gosmypiua+ vitifollum)] Sunflower (He1ianthua a+nauaa) Jerusalem artichoke () iallanthus tub@rosua
) Rubber Tsuki () iev@a brasill・aSim
) Large 9 + () 1 ord@um vulgare ) Humului 1upulu @ Ipomoea batata * Onigurumi ( Juglana regim ) Laatuca 5aliva ( Laatuca 5aliva ) Lentil (
L@! ill aallnarlm ) Ama (Llnu
Tomato (L)
yeoparsicon 1ycop*raleu
m) Malus spp, Manihot emculenta
Madjcago 5aliva
) M*ntha pip@rita ) Muma app, N1aotiana tabacum (N, r
ustlcm)) Olive (01ea auropa@
a) Rice (0ryza 5atlva) Millet (Pa+xlcum ml liaceum) Azuki (Phaseolua 1unatua) Cowpea (Phageolus mungo) Cowpea (Phageolus mungo)
Phageolus vulgaris) parsley (P
ann1a@tum glauaum) Petrothelium crispus (var. Tuberosum) (Pstrose
llnum erlspum spp, tubero
sum) Spruce (Plc@a abias) Ables alba (Pinus spp,) Plum sativum (Prunus av lum) Apricot (Prunu)
s domestic A) pu kX, 1. Darcis (
Prunus duleim) Peach (Prunus duleim)
p@rsLaa) Pyrus aommunl
m) Currant (Rlbes 5ylvesLr*) Hawthorn (Rlbes va-crlmpa) Castor bean (Relnus aommunlg) Sugarcane (5aeaharuto ofjlainarum)
Rye (Beetle a@r@al*) Rubber (S
esamue+ indreum) Potato (Sc
lanam tube@roium) Sorokoshi [f3o
rgbum bleolor (1, yulgar) Sorghum doehna
) Hokurensoku (8p1t+aaia ol@rac@
a) Cacaono+? (Th@obroma caca
o) Trlfollum pra
t*ns@) Wheat (Trltlaum mestlvu)
m) Vsoolnium aorymb
osum) Cowberry (Viooinium vial)
g-1daea) Vlcia faba
) Vigna sinensis (var. Unguiculata) (VI
Irn* m1nensis (V, unguiel
aLa) ) Grape (Vltis vlnlf*ra
) Maize (Z@a mays) New substituted cyclohexenone n-conductors are used to expand the action spectrum and to exploit synergistic effects.
Other herbicidal or plant growth regulating active substance groups can be mixed and co-sprayed with a number of different substances. The temperature of the mixed component is, for example, diazine, 4H to 3. L-
Benzoxazine derivative, benzothiadiazinone, 2,
6-sinitroaniline, N-phenyl carbamate, thiol carbamate, halogen carboxylic acid, triazine, amide, urea, diphenyl ether A/, toIJ 7-
Examples include dinone, crasil, benzofuran derivatives, quinoline-carboxylic acid and others.

Furthermore, the cyclohexenone derivatives of formula I or herbicides containing said derivatives alone or in combination with other herbicides may be used for controlling further plant protection agents, such as pests or phytopathogenic fungi or fungi. It may be advantageous to mix it with a drug and spray it neatly. Furthermore, miscibility with mineral salt solutions used to replenish nutritional and trace element deficiencies is also important. It is also possible to add non-phytotoxic oils and oil fines.

Claims (12)

[Claims] (1) Formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, A has 5 to 12 ring members fused with one or two oxirane or thiirane rings, and represents a cycloalkyl group optionally substituted by up to 4 methyl groups and bridged by an alkylene chain with up to 3 carbon atoms, R^1 being a hydrogen atom, a methoxycarbonyl group or represents a cyano group, R^2 represents an alkyl group having 1 to 4 carbon atoms, and R^3 represents an alkyl group having 1 to 3 carbon atoms, 3 or 4 carbon atoms and 1 to 3 carbon atoms; a halogenalkyl group or propargyl group having halogen atoms] and salts thereof. (2) The cyclohexenone derivative according to claim 1, wherein in formula I, R^1 is a hydrogen atom. (3) in formula I, A has 5 to 8 ring members fused with one or two oxirane or thiirane rings and may be substituted by up to 4 methyl groups; and Maximum 3
Claim 1 represents a cycloalkyl group bridged by an alkylene chain having up to
Cyclohexenone derivatives described in Section 1. (4) The cyclohexenone derivative according to claim 1, wherein in formula I, A represents a 3,4-epoxycyclopentyl group. (5) The cyclohexenone derivative according to claim 1, wherein R^2 in formula I represents an alkyl group having 2 or 3 carbon atoms. (6) Formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A has 5 to 12 ring members fused with one or two oxirane or thiirane rings, and represents a cycloalkyl group optionally substituted by up to 4 methyl groups and bridged by an alkylene chain with up to 3 carbon atoms, R^1 being a hydrogen atom, a methoxycarbonyl group or represents a cyano group, R^2 represents an alkyl group having 1 to 4 carbon atoms, and R^3 represents an alkyl group having 1 to 3 carbon atoms, 3 or 4 carbon atoms and 1 to 3 carbon atoms; In the method for producing cyclohexenone derivatives and salts thereof represented by the following formula (representing a halogen alkyl group or propargyl group having halogen atoms), formula II: ▲Mathematical formula, chemical formula, table, etc.▼
(II) [In the formula, A, R^1 and R^2 represent the above]
When a compound represented by (a) is combined with an ammonium compound of the formula: R^3O-NH_3Y [wherein R^3 represents the above and Y represents an anion] in an inert diluent, (b) in the presence of water at a temperature of 0 to 80 °C in the presence of a base, or (b) optionally present in an aqueous solution, with the formula: R^3O-NH_2 [wherein R^3 is A method for producing a cyclohexenone derivative, which is characterized by reacting it with hydroxylamine represented by the following formula in an inert solvent. (7) Formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A has 5 to 12 ring members fused with one or two oxirane or thiirane rings, and represents a cycloalkyl group optionally substituted by up to 4 methyl groups and bridged by an alkylene chain with up to 3 carbon atoms, R^1 being a hydrogen atom, a methoxycarbonyl group or represents a cyano group, R^2 represents an alkyl group having 1 to 4 carbon atoms, and R^3 represents an alkyl group having 1 to 3 carbon atoms, 3 or 4 carbon atoms and 1 to 3 carbon atoms; A herbicide containing a cyclohexenone derivative and its salt as an active substance, represented by a halogen alkyl group or a propargyl group having halogen atoms. (8) Inert additives and formula I: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A is a 5 to 12 ring member fused with one or two oxirane or thiirane rings. and represents a cycloalkyl group bridged by an alkylene chain having up to 3 carbon atoms and optionally substituted by up to 4 methyl groups, R^1 is a hydrogen atom , represents a methoxycarbonyl group or a cyano group, R^2 represents an alkyl group having 1 to 4 carbon atoms, and R^3 represents an alkyl group having 1 to 3 carbon atoms, 3 or 4 carbon atoms and a halogenalkyl group or propargyl group having 1 to 3 halogen atoms] and a salt thereof. (9) A has a 5- to 8-membered ring fused with one or two oxirane or thiirane rings, and may be substituted with up to 4 methyl groups and has up to 3 carbon atoms Herbicide according to claim 8, which contains a cyclohexenone derivative of the formula I representing a cycloalkyl group bridged by an alkylene chain with atoms. (10) The herbicide according to claim 8, which contains a cyclohexenone derivative of formula I in which R^1 represents a hydrogen atom. (11) Herbicides according to claim 8, which contain cyclohexenone derivatives of the formula I in which R^2 represents an alkyl group having 2 or 3 carbon atoms. (12) Formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, A has 5 to 12 ring members to which one or two oxirane or thiirane rings are fused, and represents a cycloalkyl group optionally substituted by up to 4 methyl groups and bridged by an alkylene chain having up to 3 carbon atoms, R^1 being a hydrogen atom, a methoxycarbonyl group or a cyano group, and R^2 represents an alkyl group having 1 to 4 carbon atoms.