JPS63139147A - 2-(2-substituted benzoyl)-4-(substituted)- 1,3-cyclohexanediones - 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 This invention relates to 2-(2-substituted benzoyl)-4-(substituted)-1,3-cyclohexanediones and their use as herbicides.

One embodiment of this invention provides herbicidally active 2-(
2-substituted benzoyl) 4 (iii)-1,3
- A herbicidal composition comprising cyclohexanedione and an inert carrier therefor. The 5-, 6- and 4-positions of the 1<3-cyclohexanedione moiety are preferably substituted with groups as defined below, most preferably with halogen or methyl groups. The benzoyl moiety may preferably be substituted with groups restated below.

Novel compounds having the following structural formula are embodied within the scope of this invention.

p-electrode Rb where R is halogen, preferably chlorine or bromine ic
+ C2 alkyl, preferably methyl; p+ c2
Alkoxy, preferably methoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; CI C
2haloalkyl; preferably trifluoromethyl, R
"5Ofi - where n is 0 or 2, preferably 2 and R1
is C, -C, alkyl, preferably methyl, trifluoromethyl or difluoromethyl. Preferably,
R is chlorine, bromine, CI C2 alkyl, C, -C2 alkoxy, trifluoromethyl, cyano, nitro, CI
C2 alkylthio or CI C2 alkylsulfonyl; more preferably chlorine, nitro, methyl, triflumethyl or methylsulfonyl. R1 is hydrogen; c+C4 alkyl, preferably methyl; halogen, phenyl; or substituted phenyl. R2 is hydrogen or C,-C4 alkyl, preferably methyl, or R
1 and R2 together are Cz'-5 alkenyl. R
3 is hydrogen; CI C4 alkyl, preferably methyl; phenyl or substituted phenyl, with the proviso that R1 and R3 are both not phenyl or substituted phenyl. R
4 is hydrogen or CI-C4 alkyl, preferably methyl, and R5 is hydrogen, halogen or auto-04 alkyl, preferably methyl. Rb is halogen, nitro, cyano,
trifluoromethyl, -C(O)-ORc where Rf
is C, -C4 alkyl, -C(O)NR2ko\, where Rb is hydrogen or CI Ca alkyl. R7 and R
8 is independently (11 hydrogen; (2) halogen; preferably,
Chlorine, fluorine or bromine; (31C, -Ca alkyl, preferably methyl; (4) CI C4 alkoxy; preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (81CI-C4 haloalkyl,
More preferably trifluoromethyl, (91Rb5O
, - where n is an integer 0. or 2, preferably 2, R
b is (al CIC4 alkyl; preferably methyl; (
b) Cl-04 alkyl substituted with halogen or cyanide, preferably chloromethyl, trifluoromethyl, or cyanomethyl; (c) phenyl; or (dlbenzyl). 001-NRcRc\ where Rc and Rd are independently hydrogen or CI C4 alkyl; (II
) ReC(O)-,: -TeR'' is C, -C4,7J
Or Cl-04 alkoxy; Q21-
SO2NRcRd where Rc and Rd are defined; or (12))-N(Rc)C(O)Rc
, where Rc and Rd are defined; ] Preferably R7 is in the 3-position. More preferably, R
7 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, ClC4 alkoxy, or ClC4 thioalkyl. Most preferably R7 is hydrogen. Re is preferably in the 4-position. Most preferably R8 is hydrogen, cyano, trifluoromethyl, or Rb5O□. Here Rb is CI-04 alkyl, preferably methyl or CI Ca haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term “CI Ca alkyl” refers to methyl, ethyl,
Includes n-propyl, isopropyl, n-butyl, 5ec-butyl, iso-butyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term “CI Ca alkoxy” means methoxy, methoxy, n-propoxy, isopropoxy, n
-butoxy, 5ec-butoxy, iso-butoxy, and t-butoxy.

The term "CI C4 haloalkyl" includes alkyl groups as defined above under C, -C4 alkyl, in which one or more hydrogens are replaced by chlorine, bromine, iodine and fluorine.

Salts of the compounds described above (as hereinafter defined) are included within the scope of this invention.

Due to tautomerism, compounds of the invention can have four structural formulas:

Here, R, Rc, R2, R3, R4, R5, R6, R7
and R11 are as defined above.

The circled proton of each of the four tautomers is moderately unstable. These protons are acidic and can be removed by reaction with a base. Then, create a salt with the following four resonance type anions.

Here, R, Rc, R2, R3, R4, R5, R6, R7
and R8 are as defined above.

Examples of these base cations are alkali metals, namely lithium, sodium and potassium; alkaline earth metals, namely calcium and magnesium; or inorganic cations such as ammonium, or where the substituents are aliphatic or aromatic. Organic cations such as the group groups substituted ammonium, sulfonium, sulfoxonium or fosquinium.

In considering the salts of this invention, those skilled in the art will recognize that various degrees of association between the anion and cation exist, depending on the nature of the cation. For example, with a suitable cation such as copper, the salt can exist in chelated form.

The compounds of this invention and their salts are active herbicides of the -C type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable plants of the present invention consists of applying a herbicidally effective amount of the above-described compounds, or salts thereof, to the location where control is desired.

The compounds of the invention can be prepared by the following two-step or, if necessary, three-step general method.

The process proceeds through the formation of an enol ester intermediate, as shown in reaction (1). The final product is the reaction (2
) or, if necessary, by rearrangement of the enol ester as shown in reaction (3).
2) by subsequent halogenation of the product obtained in step 2).

The process is carried out with respect to the enol ester in the presence of a source of cyanide anion or a catalytic amount of hydrogen cyanide, with a moderate molar excess of base.

Reactions (1) and (2) can be carried out by isolation and recovery of the enol ester using conventional techniques before carrying out step (2), or by adding a cyanide source to the reaction medium after the formation of the enol ester. or in one step by inclusion of a cyanide source at the start of reaction (1), which may be carried out as separate steps.

where R to R8 and the moderate base are defined, Y is halogen, preferably chlorine, -C4alkyl-C(O)-0-1C+ Caalco and R1
1 is the same as in the reactants shown above and the medium base is defined, preferably triC+
Cb algylamine, alkali metal carbonate or alkali metal phosphate.

Generally, molar amounts of dione and substituted benzoyl reactants are used in step (1), along with a molar amount or excess of base. The two reactants are methylene chloride,
Coupled in an organic solvent such as toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant is preferably added to the reaction mixture under cooling. The mixture is stirred at 0°C to 50°C until the reaction is substantially complete.

17″ R′ *-Cyanide Source where the moderate base and R to R8 are as defined above.

Generally, in step (2), the moles of enol ester intermediate are 1 to 4 moles of moderate base, preferably about 2 moles of moderate base and 0.01 moles to about 0.5 moles of cyanide source. or more, preferably about 0
．． 01 to 0.1 mol. The mixture is stirred in the reaction bottle at a temperature below 50°C, preferably from about 20°C to about 40°C, until the rearrangement is substantially complete. The desired product is then recovered by conventional techniques.

Alternatively, certain compounds of this invention may be prepared by the following reaction.

with X in R, R, Rc, R2, R3, R4, R5, R7 and R
8 is as defined above and R6 is halogen.

-i, in step (3), the molar amount of 2-(2-substituted benzoyl)-1,3-cyclohexadione is such as methylene chloride? To the container? It will be tolerated.

With suitable external cooling, such as a dry ice-isopropanol bath, a 1 to 3 molar amount of a halogenating reagent, such as bromine, is added at the 4- or 6-position on the 1,3-cyclohexanedione moiety, It can be added with or without a solvent to form a compound with 3 halogens. Additional moles of halogenating reagent are used for each additional halogen substituent desired. To have an additional halogenation of R; or R5, these groups must be hydrogen in the precursor. The reaction mixture was then prepared at room temperature from 1 to
Stir for 8 hours. The product is removed by conventional techniques.

The term "cyanide source" means a substance consisting of or generated under rearrangement conditions of hydrogen cyanide and/or cyanide anions.

Preferred cyanide sources are alkali metal cyanides such as sodium cyanide and potassium cyanide; cyanohydrins of methyl alkyl ketones having 1 to 4 carbon atoms in the alkyl group, such as acetone or methyl isobutyl ketone cyanohydrin; benzaldehyde cyanohydrin; Cm-c such as acetaldehyde cyanohydrin, propiosialdehyde cyanohydrin, etc.
cyclohexanone cyanohydrin; lactonitrile; zinc cyanide; di- and tri(lower alkyl)silyl cyanide, especially dimethyl- and trimethylsilyl cyanide; potassium ferrocyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered the most advantageous. This is because it produces a relatively quick reaction and is not expensive. Among the cyanohydrins, a preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in amounts up to about 50 mole percent for the enol ester. On a small scale, small amounts such as about 1 mole % may be used to produce an acceptable rate of reaction at about 40°C. Large scale reactions give more reproducible results at slightly higher catalyst levels of about 2 mole percent. Generally, about 1-10 mole percent of the cyanide source is preferred.

The process is carried out with a moderate molar excess of base with respect to the enol ester. By the term "moderate base" we mean that the strength or activity as a base differs between strong bases such as hydroxide (which can result in hydrolysis of enol esters) and N,N-dimethylaniline (which cannot function effectively). It refers to substances that act as bases, such as those found in weak bases such as wax. Moderate bases suitable for use in this embodiment include organic bases, ie, trialkylamines such as triethylamine, and inorganic bases, alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, especially potassium cyanide, a phase transfer catalyst will be involved in the reaction. Particularly suitable phase transfer catalysts are crown ethers.

A number of solvents are useful in this step, depending on the nature of the acid halide or acylation product.

The preferred solvent for this reaction is 1,2-dichloroethane. Other solvents that may be used, depending on the reactants or products, include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl butyl ketone (MIBK).

Generally, depending on the nature of the reactants and cyanide source, rearrangement will be carried out at temperatures up to about 50°C.

The substituted benzoyl chloride described above can be prepared using a gold formation reagent (
Reagents for Organic 5ynt
hesis, Vol. L, F, Fiestr
and M, Fieser, pp 767-769
(1967)) from the corresponding substituted benzoic acids.

where R, R7 and R8 are defined previously.

Substituted benzoic acids are carboxylic acids and esters chemistry S, P
atai+ editor, T, Wiley an
d 5ons, New York.

Pearson, T., Wiley and 5on
(1970)).

The following methods are three representative examples of the methods described therein.

Here, R, R? and R8 are as previously defined.

In reaction (a), a substituted benzonitrile is heated under reflux with an aqueous sulfuric acid solution for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques.

R, , R7 and R8 were defined previously.

In reaction (b), substituted acetophenone is heated under reflux with an aqueous hypochlorite solution for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques.

II R7 and R8 are defined previously.

In reaction (c), substituted toluene is heated under reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product isolated by conventional techniques.

The substituted 1,3-cyclohexanediones described above can be prepared using Modern Synthetic Reactions.
ctions.

2nd Edition, Chap, 9. H・0
・House, W ・A ・nj.

Beamtr++ Inc,, Menlo Pa
R.K., CA (1972)] and] Bisohisan,
Chem 679.9 (1964) (Liebigs Ann, Chem, 679.9 (1964) V
on ) tans Machleidtand Val
entine) lartmann).

The following examples teach the synthesis of representative compounds of this invention.

[Liebigs An Chemi
n.

Chem, ) 679. 9 (1964)] 0.5 g of 5,5-dimethyl-4-fluoro-1,3-cyclohexanedione (O,0
(12) 2 mol) and pyridine 0.25 g (O,0
(12) 2 mol) is methylene chloride 20mβ at room temperature
was dissolved in

2-nitro- dissolved in 20 ml of methylene chloride
4-trifluoromethylhenzoyl chloride 1.0g
(9 mol of O,0(12)) was added gradually with cooling.

The reaction mixture was stirred at room temperature for 24 hours, then washed twice with water, once with saturated aqueous sodium bicarbonate, and again with water. The aqueous phase was discarded and the organic phase was dried with MgSO4. and evaporation to yield the intermediate enol ester, 5,5-dimethyl-6-fluoro-3-(2-nitro-4-trifluoromethylbenzoyloxy)cyclohex-2-enone. 5
．． 5-dimethyl-6-fluoro-3-(2-nitro-4
-trifluoromethylbenzoyloxy)cyclohex-2-enone was dissolved in 30 ml acetonitrile,
0.7 g (O,007 mol) of triethylamine was added all at once. Then 0.05 g (0,0006 moles) of acetone cyanohydrin was added. The solution was stirred for 24 hours. The solvent was evaporated and the residue was washed with diethyl ether to give the product.

Dione υ 11.2 g (O, 1 mol) of 1,3-cyclohexanedione and 23.3 g (O, 1 mol) 2-chloro-4-methanesulfonylhenzoyl chloride were dissolved in 200 mj2 of methylene chloride at room temperature.

1 g (O, 11 mol) of triethylamine was added slowly under cooling. The reaction mixture was stirred at room temperature for 5 h and
1%1-HC/! was injected into. The aqueous phase was discarded and the organic phase was dried over MgSO4 and then evaporated to give the intermediate enol ester 3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone. 3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone was dissolved in 200 mβ acetonitrile and 22 g of triethylamine (
0.8 g (0.01 mole) of acetone cyanohydrin was added immediately. The solution was stirred for 5 hours, then poured into 2N-H (J!) and extracted twice with ethyl acetate. The organic layer was dried over MgSO4 and the solvent was evaporated to give the product.

-L3-dione 1Ir 2-(2-chloro-4-methanesulfonylbenzoyl)
-cyclohexane-1,3-dione 6.6 g (O,02
mole) was dissolved in methylene chloride 50 "β. Bromine 2.9 dissolved in methylene chloride 50 m7!
g (O, 018 mol) was added dropwise over 75 minutes to the solution cooled in a dry ice-isopropanol bath. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours.

The reaction mixture was then concentrated under reduced pressure to yield 8.5 g of the desired product as a semi-solid. This was confirmed by nuclear magnetic resonance, infrared spectroscopy and mass spectroscopy. The product can be further purified by column chromatography.

The table below is a list of certain selected compounds that can be prepared by the process described herein. A compound number is assigned to each compound and is used throughout the remainder of the application.

Screening Test As previously noted, the compounds described above produced by the method described above are phytotoxic compounds that are useful and valuable in controlling various plant species. . Selected compounds of this invention were tested as herbicides in the following manner.

The day before treatment, seven weed seeds were sown in loamy sandy soil in individual furrows using one seed per furrow traversed in a hand box. The seeds used were green foxtail (FT) (Se
taria viridis), water glass (Wa
ter-grass) (WG) (Echinochlo
a crusgal↓D-, wild oat-(Wi
ld oat) (WO) (Avena-Latua)
, annual morning glory
rningglory) (AMC) (IseimiヱL Hata μ
decoy target sand, velvetleaf
)) (νL) (abutilon the hr
astiL Indian mustard
mustard (MD) iuncea), and yellow nutsedge (MD)
YNG) C false thousand and rus esculentur). Numerous seeds are planted to give about 20 to 40 seedlings per furrow after germination, depending on plant size.

Using an analytical balance, 600 mg of the compound to be tested is weighed onto glassine weighing paper. 60 for paper and compounds
Place in a 1 mL transparent bottle and add 45 mL of acetone or substitution solvent.
Dissolved in j+. 18mA of this solution is 60mj! Transfer to a large transparent bottle and add 22 m of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier! diluted with 0.5% (V
/V) giving a final solution. The solution is then sprayed into the planted hand boxes on a linear spray table calibrated to deliver 80 gallons per acre (748 C/ha). The application rate is 4 pounds/knee car (4,48
kg/ha).

After processing, the hand box was heated from 21.1°C (70'F) to 26.0°C.
Plants are placed in a greenhouse at a temperature of 7"C (80'F) and irrigated with a water sprinkler. Two weeks after treatment, the degree of damage or control is determined by comparison to treated control plants at the end of the interrogation. A damage rating from 0 to 100% is recorded for each type as % control, with 0% indicating no damage and 100% indicating complete control.

The results of the test are shown in the following table ■.

Table-1 Pre-emergence herbicide activity Application rate - 4,48kg/ha Table Continued A dash (-) indicates not tested.

'7. Test: This test is conducted in the same manner as the test treatment method for the pre-emergence herbicide test, except that the seven weed seeds were planted 10-12 days before treatment. Also, irrigation of treated seed boxes is limited to the soil surface and is not applied to the leaves of germinating plants.

The results of the post-emergence herbicide tests are shown in Table ■.

Table■ Post-emergence herbicide activity Application rate - 4,48kg/ha Table Continued A dash (-) indicates not tested.

The compounds of the present invention and their salts are useful as herbicides. and can be applied at different concentrations and in different ways.

In practice, the compounds or salts may be incorporated into herbicidal compositions for agricultural use by admixture with herbicidally effective amounts of adjuvants and carriers commonly used to facilitate the dispersion of the active ingredient. It recognizes the fact that the mode of application and formulation of toxic substances influences the activity of the substance in a given application. In this way, these active herbicidal compounds or salts can be formulated as wettable powders, as emulsions, or as relatively large granules.

Memae Heavy Miscellaneous-K, Grass Test Several compounds were added to 1 bond/knee car (1.12 kg).
/ha) was evaluated for pre-emergence activity against a large number of weed seeds.

The process was similar to the pre-emergence herbicide test described in Section 2, except that only 150 mg of test compound was weighed and the application rate was 40 gallons/acre (374 A/ha).

Redroot pigweed
eed) (PW) were excluded in this test. The following weed seeds were then added:

Table ■ Pre-emergence multiple weed herbicide test application rate - 1.12 kg/ha A dash (-) indicates that it was not tested.

The above-mentioned several compounds have been added to 1 bond/knee car (1.12 kg/
The post-emergence activity was evaluated on a number of weed seeds used in pre-emergence multiple herbicide tests at application rates of ha).

The process was similar to the post-emergence herbicide Tes I• described above, except that only 150 mg of test compound was weighed and the application rate was 40 gallons/keeker.

The results of 1 and 12 kg/ha test 1~ are shown in Table ■.

Table V Post-emergence multiple weed herbicide test application rate - 1.12 kg 7 ha A dash (-) indicates not tested.

The compounds of the present invention and their salts are useful as herbicides. It can be applied in various concentrations and in various ways. In practice, the compounds or salts are formulated into herbicidal compositions by admixture in herbicidally effective amounts with carriers and adjuvants commonly used to facilitate the dispersion of the active ingredient for agricultural applications. Ru. It is a recognized fact that the formulation and mode of application of the poison will not affect the activity of the substance in a given application. Thus, these active herbicidal compounds or salts can be formulated as relatively large granules, as wettable powders, as emulsions, as powders, as flow agents, as solutions, or in any of the known types of formulations. depending on the desired mode of application. These preparations are
Depending on the weight of the active ingredient, it may contain as little as about 0.5% to as much as about 95% or more. Herbicidally effective amounts will depend on the nature of the seeds or plants being controlled, with application rates ranging from about 0.01 pounds to about 10 pounds per acre, preferably from about 0.02 pounds to about 4 pounds per acre. Change.

Wettable powders are in the form of finely divided particles that disperse readily in water or other dispersants. Wettable powders are ultimately applied to the soil as dry powders or as dispersions in other liquids. Typical carriers for hydrating agents are Fuller's earth,
Contains kaolin clay, silica and other readily wettable organic and inorganic diluents. Typically, wettable powders are formulated to contain from about 5% to about 95% active ingredient. They also usually contain small amounts of wetting agents, dispersing agents, or emulsifying agents to facilitate wetting and dispersion.

Emulsions are homogeneous liquid compositions that can be dispersed in water or other dispersants. It will then consist of a liquid or solid emulsifying side and an active compound or salt. Alternatively, liquid carriers such as xylene, heavy aromatic naphthales, isophorone, and other non-volatile organic solvents may be included. For herbicide applications, these emulsions are dispersed in water or other liquid carriers and usually applied as a spray to the land to be treated. The weight percent of the essential active ingredients will vary depending on the method in which the composition is applied, but generally ranges from about 0.5% to 9% by weight of the herbicide composition.
Contains 5% active ingredient.

Granules, in which the poison is carried in relatively large particles, are usually applied without dilution to the area where plant control is desired. Typical carriers for granules include sand, Fuller's earth, acpulgate clay, bentonite clay, montmorillonite clay, permiclate, perlite and other organic or inorganic substances that will absorb or be coated with poisons. There is.

Granules are usually formulated to contain from about 0.1% to about 25% of active ingredient. It may include a surfactant such as a heavy aromatic naphtha, kerosene, other petroleum distillates, or vegetable oil; and/or an adhesive such as desterine, glue or synthetic resin.

Typical wetting agents, dispersants or emulsifiers used in agricultural formulations include, for example, alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxy alcohols; esters and fatty amines; other surfactants. Includes types, many of which are available for purchase.

When used, surfactants usually comprise from 0.1% to 15% by weight of the herbicide composition.

Powders are free-flowing mixtures of active ingredients with organic and inorganic solids and finely divided solids such as talc, clay, and powder that act as dispersants and carriers for toxicants, making them useful formulations for soil-incorporated applications. It is.

Pastes, which are homogeneous suspensions of finely divided toxic substances in a liquid carrier such as water or oil, have been used for specific purposes. Typically these preparations contain approximately 5% of active ingredient by weight.
to about 95%, and may also contain small amounts of wetting agents, dispersing agents, or emulsifying agents to facilitate dispersion. For application, the paste is usually diluted with O and applied to the affected areas as a spray.

Other useful formulations for herbicide applications include simple solutions of the active ingredient in thoroughly dispersing agents such as acetone, alkylated naphthalenes, xylenes, and other organic solvents at the desired concentration. .

Pressurized sprays, typically aerosols, in which the active ingredient is dispersed in finely divided form as a result of evaporation of a low-boiling dispersed solvent carrier such as Freon may also be used.

However, power duster,
boom, hand 5
as a powder or spray,
Alternatively, the composition may be applied from an airplane by rope wick application. To alter or control the growth of seed germination or seedling development, powdered and liquid compositions are typically applied to the soil by a boat method and applied to the soil at a depth of at least 2 inches below the soil surface. can be distributed inside. There is no need for the phytotoxic composition to be mechanically mixed with soil particles. This is because these compositions can be applied by spraying or sprinkling onto the soil surface. The phytotoxic compositions of this invention can also be applied by addition to the irrigation water supplied to the field being treated. This method of application allows penetration of the composition into the soil as water is absorbed into the soil. Powdered, granular, or liquid compositions applied to the surface of the soil may be used in a manner similar to that of a powdered, granular, or liquid composition.
It can be distributed below the soil surface by common methods such as gging) or mixing operations.

In the following examples, the herbicide compound may be replaced with a herbicide salt of the compound.

When a salt is used as an active ingredient in the herbicidal composition of this invention, it is recommended to use an agriculturally acceptable salt.

The phytotoxic compositions of this invention may contain other additives, such as fertilizers, other herbicides and fungicides, as adjuvants or in combination with any of the adjuvants mentioned above. For example, fertilizers useful in combination with the active ingredient include ammonium nitrate, urea, and superphosphate.

Claims (1)

[Claims] (1) Compounds of the formula ▲ Numerical formulas, chemical formulas, tables, etc.▼ and their salts [where R is halogen; C_1-C_2 alkyl; C
_1-C_2 alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C_1-C_2 haloalkyl; R^aSO_n- where n is 0 or 2 and R
^a is C_1-C_2 alkyl; trifluoromethyl or difluoromethyl; R^1 is hydrogen, C_1-C_4 alkyl, halogen, phenyl or substituted phenyl; R^2 is halogen or C_1-C_4 alkyl. or R^1 and R^2 together are C_2-C_5 alkenyl; R^3 is R
^1 and R^2 are hydrogen, C_1-C_4 alkyl, phenyl or substituted phenyl, provided that both are not phenyl or substituted phenyl; R^4 is hydrogen or C_1
-C_4 alkyl; R^5 is hydrogen, halogen, or C_1-C_4 alkyl; R^6 is halogen,
cyano, nitro, trifluoromethyl, -C(O)-O
R^f where R^f is C_1-C_4 alkyl, or -
C(O)NR^b_2 where R^b is hydrogen or C_1-
C_4 alkyl. R^7 and R^8 are independently (1) hydrogen; (2) halogen; (3) C_1-C_4 alkyl; (4) C_1-C_
4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C_1-C_4 haloalkyl; (9) R^bSO_n - where n is an integer 0, 1 or 2; and R^b is (a) C_1-C_4 alkyl; (b
) C_1-C_4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) bezyl; (11) R
^eC(O)-where R^e is C_1-C_4 alkyl or C_1-C_4 alkoxy; or (12)-SO_
2NR^cR^d where R^c and R^d are defined; and (13)-N(R^c)C(O)R^d, R
^c and R^d are defined; ] (2) R is chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R^1
, R^2, R^3, R^4 and R^5 are hydrogen or methyl; R^6 is halogen; R^7 and R^8
are independently (1) hydrogen; (2) halogen; (3) C_1-
C_4 alkyl; (4) C_1-C_4 alkoxy; (
5) Trifluoromethoxy; (6) Cyano; (7) Nitro; (8) C_1-C_4 haloalkyl; (9) R^b
SO_n- where n is an integer 0, 1 or 2; and R^b is (
a) C, -C4 alkyl; (b) C_1-C_4 alkyl substituted with halogen or cyano; (c) phenyl;
or (d) benzyl; (10)-NR^cR^d, where R^c and R^d are independently hydrogen or C_1-C_4 alkyl; (11) R^eC(O)-, where R ^e is C_1
-C_4 alkyl or C_1-C_4 alkoxy; or (12) -SO_2NR^cR^d where R^c and R
^d is defined; or (13)-N(R^c)C
The compound according to claim 1, wherein (O)R^d, where R^c and R^d are defined. (3) R^7 and R^8 are independently hydrogen; chlorine; fluorine;
Bromine; Methyl; C_1-C_4 alkoxy; Trifluoromethoxy; Cyano; Nitro; Trifluoromethyl; R
^bSO_n- where n is an integer 0 or 2 and R^b is methyl, chloromethyl, trifluoromethyl, ethyl or n-propyl; R^eC(O)- where R^e is C_1-C_4 alkyl; or SO_2NR^cR^d, where R^c and R^d are defined; and; R^7 is in the 3-position and R^8 is in the 4th position. Claim 2 Compounds described in Section. (4) A method for controlling undesirable plants comprising applying a herbicidally effective amount of a compound of the formula ▲ (numerical formula, chemical formula, table, etc.) and salts thereof to the location where control is desired. [Here, R is halogen; C_1-C_2 alkyl; C
_1-C_2 alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C_1-C_2 haloalkyl; R^aSO_n- where n is 0 or 2 and R
^a is C_1-C_2 alkyl; trifluoromethyl or difluoromethyl; R^1 is hydrogen, C_1-C
_4 is alkyl, halogen, phenyl or substituted phenyl; R^2 is hydrogen or C_1-C_4 alkyl; or R^1 and R^2 together are C_2-C_5 alkylene; R^3 is Hydrogen, C_1-, provided that R^1 and R^2 are both not phenyl or substituted phenyl.
C_4 is alkyl, phenyl or substituted phenyl; R
^4 is hydrogen or C_1-C_4 alkyl; R^5
is hydrogen, halogen or C_1-C_4 alkyl;
R^6 is halogen, cyano, nitro, trifluoromethyl, -C(O)-OR^f where R^f is C_1-C_
4 alkyl; or -C(O)NR^b_2 where R^b
is hydrogen or C_1-C_4 alkyl; R^7 and R^8 are independently (1) hydrogen; (2) halogen; (3)
C_1-C_4 alkyl; (4) C_1-C_4 alkoxy; (5) trifluoromethoxy; (6) cyano; (
7) Nitro; (8) C_1-C_4 haloalkyl; (9
) R^bSO_n - where n is an integer 0, 1 or 2; and R^b is (a) C_1-C_4 alkyl; (b) C_1-C_4 alkyl substituted with halogen or cyano; (
c) phenyl; or (d) benzyl; (10)-NR^
cR^d Here, R^c and R^d are independently hydrogen or C_
1-C_4 alkyl; (11) R^eC(O)- where R^e is C_1-C_4 alkyl or C_1-C_4 alkoxy; or (12)-SO_2NR^cR^d where R^c and R^d is defined; and (13) −
N(R^c)C(O)R^d where R^c and R^d are defined; ] (5) R is chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R^1, R^2, R^3, R^4
and R^5 is hydrogen or methyl; R^6 is hydrogen; R^7 and R^8 are independently (1) hydrogen; (2) halogen; (3) C_1-C_4 alkyl; (4) C_1-
C_4 alkoxy; (5) trifluoromethoxy; (6
) cyano; (7) nitro; (8) C_1-C_4 haloalkyl; (9) R^bSO_n- where n is an integer 0 A1 or 2; and R^b is (a) C_1-C_4 alkyl; (b) C_1 substituted with halogen or cyano
-C_4 alkyl; (c) phenyl; or (d) benzyl; (10) -NR^eR^d where R^c and R^d
are independently hydrogen or C_1-C_4 alkyl; (11) R
^eC(O)-where R^e is C_1-C_4 alkyl or C_1-C_4 alkoxy; or (12)-SO_
2NR^cR^d where R^c and R^d are defined; or (13)-N(R^c)C(O)R^d where R^c and R^d 5. The method of claim 4, wherein: is defined. (6) R^7 and R^8 are independently hydrogen; chlorine; fluorine;
Bromine; Methyl; C_1-C_4 alkoxy; Trifluoromethoxy; Cyano; Nitro; Trifluoromethyl; R
^bSO_n- where n is an integer 0 or 2 and R^b is methyl, chloromethyl, trifluoromethyl, ethyl or n-propyl; R^eC(O)- where R^e is C_1-C_4 alkyl; or SO_2NR^cR^d, where R^c and R^d are defined; and; R^7 is in the 3-position and R^8 is in the 4-position. Claim 7 The method described in section. (7) Herbicidally active 2-(2-substituted benzoyl)-
A herbicidal composition comprising 4-(substituted)-1,3-cyclohexanedione or a salt thereof and an inert carrier. (8) 2-(2-substituted benzoyl)-4-(substituted)-1
, 3-cyclohexanedione is a compound of the formula ▲ which has a mathematical formula, chemical formula, table, etc. ▼ and salts thereof. [Here, R is halogen; C_1-C_2 alkyl; C_
1-C_2 alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C_1-C_2 haloalkyl; R^aSO_n- where n is 0 or 2 and R^
a is C_1-C_2 alkyl; trifluoromethyl; or trifluoromethyl; R^1 is hydrogen, C_1-
C_4 alkyl, halogen, phenyl, or substituted phenyl; R^2 is hydrogen or C_1-C_4 alkyl. Or R^1 and R^2 together are C_2-C_5 alkylene. R^3 is hydrogen, C_1-, with the condition that R^1 and R^3 are both phenyl or substituted phenyl.
C_4 alkyl, phenyl or substituted phenyl. R
^4 is hydrogen or C_1-C_4 alkyl; R^5 is hydrogen, halogen or C_1-C_4 alkyl; R^6
is hydrogen, cyano, nitro, trifluoromethyl, -C(
O)-OR^f where R^f is C_1-C_4 alkyl; or -C(O)NR^b_2 where R^b is hydrogen or C_1-C_2 alkyl. R^7 and R^8 are independently (1) hydrogen; (2) halogen; (3) C_1-C_
4 alkyl; (4) C_1-C_4 alkoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro;
(8) C_1-C_4 haloalkyl; (9) R^bSO
__n - where n is an integer 0, 1 or 2; and R^b is (a
) C_1-C_4 alkyl; (b) C_1-C_4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10)-NR^cR^d where R^c and R^ d is independently hydrogen or C_1-C_4 alkyl; (11) R^eC(O)- where R^e is C_
1-C_4 alkyl or C_1-C_4 alkoxy; or (12)-SO_2NR^cR^dR^c and R^d
is defined; and (13)-N(R^c)C(O
) R^d, R^c and R^d are defined; ] (9) R is chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R^1
, R^2, R^3, R^4 and R^5 are hydrogen or methyl; R^6 is halogen; R^7 and R^8 are independently (1) hydrogen; (2) halogen; (3) C_1-C_4 alkyl; (4) C_1-C_4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8
) C_1-C_4 haloalkyl; (9) R^bSO_n
- where n is an integer 0, 1 or 2; and R^b is (a)C
_1-C_4 alkyl; (b) C_1-C_4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10)-NR^eR^d, where R^c and R^ d is independently hydrogen or C_1-C_4 alkyl; (11) ReC(O)-, where R^e is C_1
-C_4 alkyl or C_1-C_4 alkoxy; or (12)-SO_2NR^cR^d, where R^c and R^d are defined; or (13)-N(R^c)
9. The composition of claim 8, wherein C(O)R^d, where R^c and R^d are defined. (10) R^7 and R^8 are independently hydrogen; chlorine; fluorine; bromine; methyl: C_1-C_4 alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl;
R^bSO_n - where n is an integer 0 or 2 and R^b is methyl, chloromethyl, trifluoromethyl or n-propyl; R^eC(O)-, R^e is C_1-C_4 alkyl; or SO_2NR ^cR^d Here, R^c and R^d are defined; R^7 is in the 3-position, R
10. The composition of claim 9, wherein ^8 is in the 4-position. (11) Herbicidally active 2-(2-substituted benzoyl)
A method for controlling undesirable plants comprising applying a herbicide composition comprising -4-(substituted)-1,3-cyclohexanedione or a salt thereof and an inert carrier to a location where control is desired. (12) In the method for preparing compounds of the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and their salts, the method is to prepare compounds of the formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼. In step (b), reacting the substituted benzoyl reactant of formula ▼ with at least 1 mole of moderate base to form an intermediate enol ester of formula ▲ , 1 mole of enol ester to 1 mole of medium base
to 4 moles and from 0.01 moles to about 0.01 moles of cyanide source.
2-(2-substituted benzoyl)-4(substituted)-1,3-cyclohexanedione and How to prepare those salts. [Here, R is halogen; C_1-C_2 alkyl; C
_1-C_2 alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C_1-C_2 haloalkyl; R^aSO_n- where n is 0 or 2 and R^
a is C_1-C_2 alkyl; trifluoromethyl or or difluoromethyl; R^1 is hydrogen, C_1
-C_4 alkyl, halogen, phenyl or substituted phenyl; R^2 is hydrogen or C_1-C_4 alkyl. Or R^1 and R^2 together are C_2-C_5 alkylene. R^3 is hydrogen, with the proviso that R^1 and R^3 are both not phenyl or substituted phenyl.
C_1-C_4 alkyl, phenyl or substituted phenyl. R^4 is hydrogen or C_1-C_4 alkyl; R^
5 is hydrogen, halogen or C_1-C_4 alkyl. R^6 is halogen, cyano, nitro, trifluoronitro, trifluoromethyl, -C(O)-OR^f where R^f is C_1-C_4 alkyl; or -C(O)NR
^b_2 where R^b is hydrogen or C_1-C_2 alkyl. R^7 and R^8 are independently (1) hydrogen; (2
) halogen; (3) C_1-C_4 alkyl; (4) C
_1-C_4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C_1-C_4
Haloalkyl; (9) R^bSO_nn is an integer 0, 1
or 2, where R^b is (a) C_1-C_4 alkyl; (
b) C_1-C_4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10
)-NR^cR^d where R^c and R^d are independently hydrogen or C_1-C_4 alkyl; (11) R^eC(O
)-Here, R^e is C_1-C_4 alkyl or C_1
-C_4 alkoxy; or (12)-SO_2NR^c
R^d, R^c and R^d are defined; Y is halogen, C_1-C_4 alkyl-C(O)-O
-, C_1-C_4 alkoxy-C(O)-O- or ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ where R, R^7 and R^8 in this part of the molecule are the same as in the reactants shown above. ] (13) Y is chlorine and the medium base is tri-C_1
-C_6 alkylamine, pyridine, alkali metal carbonate or alkali metal phosphate, and the cyanide source is alkali metal cyanide, cyanohydrin of methyl C_1-C_4 alkyl ketone, benzaldehyde or C_2
-C_5 aliphatic aldehyde cyanohydrin; cyanohydrin; zinc cyanide; tri(lower alkyl)silyl cyanide, or hydrogen cyanide Claim 1
Preparation method according to item 2. (14) Y is chlorine, medium base is triC_1-C_6
14. The process according to claim 13, wherein the cyanide source is potassium cyanide, acetone cyanohydrin or hydrogen cyanide.