JPH0479348B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION The present invention relates to the use of 5-amino-3-oxo-4-(substituted phenyl)-2,3-dihydrofuran derivatives and compounds thereof as herbicides. Academic paper “Chemiker−Zeitung” 104
(1980) No. 10, pp. 302-303, 1-(dimethylamino)-2,4-diphenyl-1-butene-3,
The 4-dione is ring-closed to form 5-dimethylamino-
A method for obtaining 2,4-diphenyl-2,3-dihydrofuran is disclosed. British Patent No. 1521092
The specification discloses certain 3-phenyl-5-substituted-4(1H)-pyrid-ones or -thiones as herbicides. Patent Application No. 13710 (Chemical Abstracts 71:61195e) contains 5-
Describe the general formula of amino-3-oxo-4-(phenyl and halophenyl)-2,3-dihydrofuran, specifically 5-amino-3-oxo-4
-(phenyl and 4-chlorophenyl)-2,3
-dihydrofuran is disclosed. Japanese patent no.
Specification No. 19090 (Chemical Abstracts)
69p10352e) discloses 2,3-dihydrothiophenes as pharmaceuticals. “Heluetica
Chemica Acta, Volume 66, Pages 362-378 (1983)
As part of academic chemical synthesis considerations, 5-N-
Cyclopropyl-4-phenyl-2-methoxycarbonyl-methylene-3-furanone is disclosed.
US Pat. No. 4,441,910 discloses herbicidal ureidosulfonylfurans and ureidosulfonylthiophenes. SUMMARY OF THE INVENTION The present invention provides compounds that have pre- and post-emergent herbicidal activity, and in particular have good pre-emergent activity against a wide range of broad-leaved plants and weeds. The compounds of the present invention have the general formula (wherein R is a group of lower alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, lower alkenyl, 1 to 4 carbon atoms and fluorine, chlorine, bromine or iodine) haloalkyl having 1 to 3 halo atoms independently selected from;
haloalkenyl having 2 to 4 carbon atoms and 1 to 3 halo atoms independently selected from the group of fluorine, chlorine, bromine or iodine, the alkoxy and alkyl moieties independently having 1 to 3 carbon atoms; lower alkoxyalkyl having atoms, phenyl, 1-naphthyl, 1-indenyl, 4-fluorophenyl, arylalkylene having 1 to 3 carbon atoms in the alkylene part and in which the aryl part is phenyl, 1-naphthyl or 1-indenyl; , or or (In the formula, 1 of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹
, 2 or 3 are independently lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 to 3 carbons and 3 of the same or different halogen atoms, and the remainder are hydrogen; ,
R ³ is a single bond or alkylene having 1 to 3 carbon atoms), and R ¹ is hydrogen or 1 to 4
alkyl having 1 to 4 carbon atoms, R ² is hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 or 4 carbon atoms, R 2 is hydrogen, alkyl having 1 to 4 carbon atoms, and the alkyl moiety is alkoxycarbonylalkyl having 1 to 4 carbon atoms, the alkoxy moiety and the alkyl moiety are independently alkoxyalkyl having 1 to 3 carbon atoms, or the alkyl moiety is independently 1 to 3 carbon atoms.
alkylthioalkyl having 3 to 3 carbon atoms, or R ¹ and R ² together with the adjacent nitrogen atoms are
form a saturated or unsaturated nitrogen heterocycle with 5 ring atoms, one of which is nitrogen and the remainder are carbon atoms, X is hydrogen, halo or trifluoromethyl and any of the phenyl rings and Y is lower alkyl, lower alkoxy,
halo, lower haloalkyl having 1 to 4 carbon atoms and 1 to 3 identical or different halogen atoms; having 1 to 4 carbon atoms and 1 to 3 identical or different halogen atoms; lower haloalkoxy or lower haloalkylthio having 1 to 4 carbon atoms and 1 to 3 same or different halo atoms, provided that when Y is halo, R, R ¹
and R ² are not all hydrogen, and Y is other than trifluoromethyl and X is other than hydrogen, and R ¹ is hydrogen and R ³ is hydrogen, then R is methyl,
ethyl, propyl, 2-halophenyl, 2-lower alkyl phenyl or 4-fluorophenyl). The present invention also provides compatible salts of compounds of formula (), such as replacing the amino hydrogen (i.e. R ¹ and R ² are hydrogen) with a compatible cation or enolizing the 3-oxo group, followed by enolization of the 3-oxo group. Includes salts obtained by substituting amino hydrogen. Compounds of formula () exist as ketoenol isomers. This compound has an asymmetric carbon atom and can also exist as optical isomers. In some cases, the compounds also exist as geometric isomers. The above formula is intended to encompass each isomer and mixtures thereof, and each isomer and mixtures thereof are included within the present invention. It has been found that the presence of a 3-trifluoromethyl substituent on the 4-phenyl group of the compounds of the invention generally greatly enhances herbicidal activity. In another aspect, the invention provides herbicidal compositions having a compatible carrier and a herbicidally effective amount of a compound of general formula (), or a compatible salt thereof, or a mixture thereof. The present invention also provides for the suppression or control of undesirable germination growth, characterized in that the growing medium and/or such germination leaves are treated with a herbicidally effective amount of a compound of formula () and/or a compatible salt thereof. provide a method to do so. The present invention also provides chemical intermediates and methods for making compounds of formula (). The invention will now be described. Description of the invention and preferred embodiments Representative compounds of formula () of the present invention are Examples 2, 3,
This can be shown in 6-10. Regarding substituents,
Preferred compounds are: R is lower alkyl, aryl or substituted aryl, more preferably methyl, ethyl, propyl, phenyl or substituted phenyl, especially phenyl, monomethylphenyl or monohalophenyl, more especially methyl, ethyl, n-propyl,
2-halophenyl, 2-lower alkyl phenyl,
or 4-fluorophenyl, R ¹ and R ² are independently hydrogen, methyl, ethyl or n-propyl, preferably one of R ¹ or R ² is hydrogen and the other is hydrogen,
Methyl, ethyl or n-propyl, preferably hydrogen, methyl or ethyl, especially methyl, X is hydrogen and/or Y is 3-trifluoromethyl or 3-halo, especially 3-trifluoromethyl. Most desirably, the compounds contain two or more desired substituents. Compounds of formula () in which R ¹ and R ² are each hydrogen and R is aryl or substituted aryl can be advantageously prepared according to the following scheme. (wherein X and Y are as defined above, and Z' is aryl or substituted aryl) Compound (A) is converted to compound (') by:
This can be advantageously carried out by contacting compound (A) with a halogen, preferably bromine, and a liquid carboxylic acid in the presence of an inert organic solvent. Generally, this method uses approximately
Using 1.0 to 10.0 mol, preferably 1.0 to 1.1 mol of halogen, at about 0 to 100°C, preferably about 20 to 30°C.
As a suitable liquid carboxylic acid that can be used for about 4 to 36 hours, preferably about 18 to 24 hours at
Examples include acetic acid, propionic acid, butyric acid, and formic acid. By using an excess of carboxylic acid, it can serve as a solvent or liquid carrier for the reaction system. Other organic solvents that can be used include, for example, liquid halogenated alkanes such as methylene chloride, carbon tetrachloride, chloroform, 1,
These include 2-cycloethane, liquid aromatic compounds such as benzene, toluene, liquid alkyl ethers such as diethyl ether, dimethylsulfoxide, dimethylformamide, etc., and compatible mixtures thereof. Best results are obtained with bromine as the halogen, although chlorine and iodine can also be used. The starting compound of formula (A) can be prepared according to the following reaction scheme. (wherein R ¹ is lower alkyl, aryl (eg phenyl) or arylalkylene (eg benzyl) and Z', Y and X are as defined above). This method can be advantageously carried out by contacting compound (B) with compound (C) and a strong base, preferably in the presence of an inert organic solvent. Generally, about 1.0 to 10.0 per mole of compound (B)
mol, preferably 1.0 to 1.2 mol of compound (C) at about 0° to 100°C, preferably 75 to 85°C.
The process is carried out for 36 hours, preferably 18-24 hours. Generally, about 1.0 to 1 mole of compound (C)
Use 10.0 mol of base. Suitable bases that can be used include, for example, alkali metal alkanolates, such as sodium methoxide,
potassium ethoxide, sodium hydride,
Potassium hydride etc. The strong base is preferably one that does not produce water as a by-product in this reaction system. Suitable inert organic solvents that can be used include, for example:
These include lower alkanols (eg methanol, ethanol, propanol), tetrahydrofuran, dimethoxyethane, dioxane, etc. and compatible mixtures thereof. Alkali metal alkanolates are preferably prepared in situ by reacting the alkali metal with an excess of alkanol (which serves as a solvent in the above reaction). Starting materials of formulas (B) and (C) are generally known and can be prepared by known methods or modifications thereof (ie, substitution of appropriate starting materials). Compound
For example, the production of (B) is carried out in "Org.Syn.Coll.", Volume 1,
107 (1941), and the preparation of compound (C) is described in "Org.Syn.Coll.", Vol. 1, 270 (1941). Compounds of formula () in which R ¹ and R ² are each hydrogen can be prepared by the general method shown in the following reaction scheme. (wherein R ^,
). This method can advantageously be carried out by contacting compound (B) with compound (E) and a strong base (eg, sodium methoxide, sodium ethoxide), preferably in an inert organic solvent. Generally, this method uses about 1.0 to 10.0 mol, preferably 1.0 to 1.2 mol, of compound (E) per 1 mol of compound (B) at about 0 to 100°C, preferably 75 to 85°C.
It is carried out for about 5 to 36 hours, preferably 18 to 24 hours.
Suitable inert organic solvents that can be used include, for example, lower alkanols (e.g. methanol, ethanol, propanol), tetrahydrofuran,
Dimethoxyethane, dioxane, etc., and compatible mixtures thereof. Suitable bases that can be used in this method include the compound
Includes those already mentioned regarding the reaction between (B) and compound (C). Hydroxy esters of formula (E) are generally known compounds and can be prepared by known methods or obvious modifications thereof (eg using suitably substituted starting materials). Compounds of formula () where R ¹ and R ² are hydrogen and R is alkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenylalkyl (e.g. -CH ₂ CH=CH) It can also be advantageously produced using the reaction scheme shown below. (wherein R is alkyl, cycloalkyl, alkoxyalkyl, alkoxy, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenyl, and R ¹⁰ is lower alkyl, preferably methyl). This method can be advantageously carried out under reaction conditions, preferably by bringing the compound (A') into contact with a reducing agent in an inert organic solvent. Generally, this method uses about 1 to 10 mol, preferably 1 to 2 mol, of the reducing agent per 1 mol of compound (A'), and the temperature is about 0 to 200°C, preferably about 115 to 120°C.
, for about 10 to 120 minutes, preferably about 10 to 30 minutes.
Suitable reducing agents that can be used include, for example, strong anhydrous acids such as sulfuric acid, hydrochloric acid, hydrogen bromide, trifluoroacetic acid, methanesulfonic acid, and the like. Best results are usually obtained using anhydrous sulfuric acid. Suitable inert organic solvents that can be used include, for example, acetic acid, propionic acid, butyric acid, toluene, xylene, etc. and compatible mixtures thereof. The starting material of formula (A') can be prepared according to the following scheme. (wherein R and R ¹⁰ are as defined above, X' is chlorine, bromine or iodine, and M and M' are independently sodium or lithium). Although the method is illustrated as three steps, it is generally best performed in situ. As is customary for such reactions, the present method is preferably carried out under substantially anhydrous conditions under an inert gas (eg, nitrogen). In the first step of the process, compound (B') is contacted with a non-nucleophilic base, preferably in an inert organic solvent. This step is generally carried out about 1 to 2 mol, preferably 1 to 2 mol, of the non-nucleophilic base per 1 mol of compound (B').
Using 1.3 molar equivalents, the reaction is carried out at about 0 to 25°C for about 1/2 to 3 hours. Suitable non-nucleophilic bases that can be used include, for example, alkali metal hydrides such as sodium hydride, potassium hydride, etc., alkali metal amides such as lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl) ) amide,
Examples include lithium diethylamide, lithium diisopropylamide, and sodium dimethylamide.
Sodium hydride is generally preferred. This is because it gives very good results and is easily available. Alkali metal amides and, of course, alkali metal hydrides are also generally known compounds and can be prepared by known methods or obvious variations thereof. For example, an alkali metal amide can be produced by reacting a secondary amine with an alkali alkali metal. Suitable inert organic solvents that may be used are, for example, tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether, diisopropyl ether, etc. and compatible mixtures thereof. The second step can be carried out by bringing the compound (B) into contact with an alkyl base, preferably in an inert organic solvent. As mentioned above, this method step is the first
Preferably, this is done in situ with the reaction product mixture of the process. Generally, the second step is about 1 to 2 mol, preferably 1 to 2 mol, of alkyl base per 1 mol of compound (B″).
Using 1.3 molar equivalents, the reaction is carried out at about -78 DEG to 0 DEG C. for about 1 to 4 hours. Suitable alkyl bases that can be used include, for example, alkyl-alkali metals, alkyl Grignard reagents, and the like. It is preferred to use n-butyllithium because it gives good results and is readily available. Suitable solvents that can be used are those listed for the first step. The third step can be carried out by bringing the compound (B) into contact with a suitable R halide having the desired R group, preferably in an inert organic solvent. The third step is usually carried out in situ with the reaction products of the second step. The third step of this process uses about 1 to 10 moles, preferably 1 to 1.5 moles of RX per mole of B, at about -30 to 30°C, preferably 22 to 25°C, for about 1 to 18 hours, preferably 1 to It is generally done in 5 hours.
Suitable inert organic solvents include those already mentioned for the first step of the process. RX' halides are generally known compounds and can be prepared by known methods or obvious variations thereof (eg, substitution of appropriate reactants and solvents). The starting material of formula (B') can be prepared according to the scheme below. (wherein R ¹¹ is lower alkyl (preferably methyl), and R ¹⁰ , Y and X are as defined above). This method is preferably carried out by contacting compound (B), compound (C') and a strong base under reaction conditions in an inert organic solvent. In general, this process is carried out using the same conditions described above for the preparation of compound (A), except that reactant (C') is used in place of reactant (C). The reactant of formula C' is a simple alkyl alkoxy acetate ester, such as methyl methoxy acetate. Methods for making such compounds are well known in the art. A compound of formula () in which one or both of R ¹ and R ² is substituted can be produced by alkylating the amino group of a corresponding compound of formula (). (where R, R′, x and Y are as defined above, R ² ′ is as defined for R ² but is not hydrogen, and R ² ′Z″ requires dealkylation. (if the compound is an alkylating agent having a suitable R ² ' group or an R ¹ group).
This can be done by bringing them into contact. For example, for this method, compound ('') and R ² ' are desirably combined in an inert organic solvent and in the presence of a scavenger base.
This can be carried out by contacting with iodide or bromide. In general, this method uses about 0 to
It is carried out at 100°C, preferably 20-45°C, for about 1.0-72.0 hours, preferably 2.0-18.0 hours. If it is necessary to monoalkylate, generally about 1.0 to 1.1 moles of R ² ' halide reactant are used per mole of compound (''). If it is necessary to alkylate both hydrogens of the amino group, generally is the compound (″)1
About 1.9 to 4.0 moles per mole of R2 ^' halide are used. When preparing compounds in which R ² ' is alkoxyalkyl or alkylthioalkyl, an excess of R ² ' halide may be used even if monoalkylation is desired. For example, "3 to 6 moles of ^R2Z per mole". If necessary,
In the second step, further alkylation can be carried out. Variations on R ¹ and R ² can be made by first alkylating one hydrogen of the amino group and then alkylating the second amino hydrogen with an alkylating agent having a different R ² ' group. Compounds in which R ¹ and R ² together with the amino nitrogen atom form a saturated heterocycle may be prepared using a suitable Z″-(CH ₂ ) _2-5 Z″ where Z″ is a Cl or Br alkylating agent. R ¹ , R ² N unsaturated heterocycles can be prepared using suitable cis-alkenyl dihalides in which one of the halo atoms is at each terminal alkenyl carbon. Organic solvents include, for example, liquid halogenated alkanes such as methylene chloride, carbon tetrachloride or dichloroethane. Tetrahydrofuran is also useful. Suitable scavenger bases that can be used include, for example, compounds (B) and (C). ) where R ¹ is lower alkyl (e.g. methyl) and R ²
Compounds of formula () in which is hydrogen or lower alkyl are advantageously prepared using dialkyl sulfates as alkylating agents. R ¹ and/or R ²
This may advantageously be carried out by contacting a compound of the formula in which one or both of are hydrogen with the lower alkyl sulfate of interest in the presence of a strong base, preferably in the presence of a phase inverting agent, in an inert organic solvent. In general,
This method uses about 1.0 to 4.0 mol of dialkyl sulfate per 1 mol of compound (), and uses about 0 to 100 mol of dialkyl sulfate.
It is preferably carried out at a temperature of 20 to 45°C. Generally, about a 2.5 molar excess of base is used. This method is also preferably carried out in an inert organic solvent such as methylene chloride, carbon tetrachloride, dichloroethane, or tetrahydrofuran. Suitable strong bases that can be used include, for example, sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium carbonate, potassium carbonate, and the like. Suitable phase change agents are those that convert hydrophilic ions to lipophilic organic systems. Examples include benzyltriethylammonium chloride, tetra-n-butylammonium chloride, methyltrioctylammonium chloride, and the like. Compatible salts of formula () can be prepared in conventional manner, e.g.
Compounds of formula () in which R ¹ and/or R ² are hydrogen are treated with a suitable strong base (e.g. n-butyllithium,
(sodium hydride, potassium hydride, etc.) to obtain the corresponding R ¹ and/or R ² cation salts. The enolate salt has R ¹ and/or
Alternatively, it can be produced by treating the R ² cation salt with a base in a conventional manner. An alternative method for salt cations can be carried out via ion exchange with an ion exchange resin containing the cation of interest. General Reaction Conditions In the methods described above, it is generally desirable to separate each product before proceeding to the next step in the reaction process, unless described as an in-situ step or otherwise specified. These products can be recovered from each reaction product mixture by appropriate separation or purification methods such as recrystallization or chromatography. Suitable separation and purification methods are illustrated, for example, in the Examples below. Generally, the reaction is carried out as a liquid phase reaction, so pressure is generally not critical. However, when the reaction is carried out under reflux, this does not apply when the temperature (boiling point) is affected. Accordingly, these reactions are generally carried out under pressures of about 300 to 3000 mm Hg, but preferably at atmospheric or ambient pressure. It will be appreciated that other reaction conditions may be used, provided that the general or desired process conditions (eg, reaction temperature, time, molar ratio of reactants, solvent, etc.) are indicated. Optimal reaction conditions (eg, temperature, reaction time, molar ratio, solvent, etc.) may vary depending on the particular reagent or organic solvent used, but can be determined by conventional optimum methods. When obtaining a mixture of optical isomers, each optical isomer can be obtained by a conventional dissociation method. Geometric isomers can be separated by conventional separation methods based on differences in physical properties between the isomers. Definitions Terms used herein have the following meanings unless otherwise specified. "Lower alkyl" means straight-chain and branched-chain alkyl groups having from 1 to 4 carbon atoms, including primary,
Includes secondary and tertiary alkyl groups. Representative alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl. "Alkylene" means straight chain and branched alkylene groups, such as _-CH2- , _{-CH2- CH2} ,

[Formula] etc. "Lower alkenyl" means 2 to 6 carbon atoms,
It means an alkenyl group preferably having 2 to 4 atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-methylprop-1-enyl, and the like. "Lower alkoxy" means -OR ¹ group (R ¹ =lower alkyl). "Lower alkylthio" means a -SR' group (R'=lower alkyl). “Lower alkoxyalkyl” means R′, OR″−
"lower alkylthioalkyl" means a group in which R' and R" are independently straight or branched alkyl having from 1 to 3 carbon atoms. "Lower alkylthioalkyl" means R',
SR'' radical, where R' and R'' are straight-chain or branched alkyl having 1 to 3 carbon atoms. What is “lower alkoxycarbonylalkyl”?
base (R' is lower alkyl and R'' is alkylene having 1 to 4 carbon atoms, which may be straight or branched.) Representative alkoxycarbonylalkyl groups include, for example, -CH ₂ C(O)
_OCH3 , -CH( _CH3 )C(O) _{OC2H5 ,} etc. "Halo" means fluorine, chlorine, bromine and iodine. "Lower haloalkyl" means haloalkyl having 1 to 4 carbon atoms and 1 to 3 halo atoms independently selected from the group of fluorine, chlorine, bromine and iodine. Desirably, lower haloalkyl groups have 1 to 2 carbon atoms. "Lower haloalkoxy" means a "lower alkoxy" having 1 to 3 halo atoms independently selected from the group of fluorine, chlorine, bromine or iodine. "Aryl" means an aryl group having 6 to 10 carbon atoms and includes, for example, phenyl, naphthyl, indenyl. Generally, such groups are more readily available than other aryl compounds, so
Aryl groups are phenyl or naphthyl. "Substituted aryl" means 1 to 3 substituents independently selected from the group of lower alkyl, lower alkoxy, halonitro, or haloalkyl having 1 to 3 carbon atoms and 1 to 3 halo atoms. means an aryl group having Representative substituted aryl groups include, for example, 2-fluorophenyl, 2-chlorophenyl, 2,6-dimethylphenyl, 4-fluorophenyl, 2-methylphenyl, 2-chloro-
3-chloromethylphenyl, 2-nitro-5-methylphenyl, 2,6-dichlorophenyl, 3-
trifluorophenyl, 2-methoxyphenyl, 2
-bromonaphthyl-1,3-methoxyindene-
1-yl etc. "Arylalkylene" means ArR ³ - group (Ar
is aryl and ^R3 is alkylene having 1 to 3 carbon atoms, including straight chain or branched alkylene, such as methylene, ethylene, 1-methylethyl, and propylene. "(Substituted aryl)alkylene" or "ring-substituted arylalkylene" refers to the group Ar′R ³ - where "Ar′ is substituted aryl and R ³ is alkylene as defined for arylalkylene. R ¹ and What is “saturated nitrogen heterocycle” used for R ² ? (wherein n is 1, 2 or 3). What is the "unsaturated nitrogen heterocycle" used for R ¹ and R ² in the formula?

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[Formula] and Beauty

means a group having the formula; By "compatible salt" is meant a salt that does not significantly alter the herbicidal properties of the compound. Suitable salts include, for example, cationic salts such as lithium, sodium, potassium, alkaline earth metal, ammonia, quaternary ammonium bases, and the like. "Room temperature" or "ambient temperature" means about 20-25°C. Utility The compound of formula () exhibits pre-emergence and post-emergence herbicidal activity, and is particularly good in pre-emergence herbicidal activity. Generally, for post-emergence applications, the herbicidal compound is applied directly to the leaves or other plant parts. In pre-emergence applications, the herbicidal compound is applied to the growing medium or anticipated growing medium. The optimum amount of the herbicidal compound or composition will vary depending on the plant species and growth of the plant, the specific site of the plant contacted and the degree of contact.
The optimum amount used will also vary depending on the prevailing site or environment (e.g., a closed area such as a greenhouse compared to an exposed area such as the outdoors) and the type and degree of control desired. Generally, for pre-emergence and post-emergence control, the compounds should be used at about 0.02-60Kg/ha, preferably at about 0.02-10Kg/ha.
Apply at the rate of Kg/ha. Also, while in theory the compounds may be applied undiluted, in practice they are generally applied as a composition having an effective amount of the compound and an acceptable carrier. An acceptable or compatible carrier (agriculturally acceptable carrier) is one that does not significantly adversely affect the desired biological effect achieved by the active compound. Generally, the composition is approximately
Contains 0.05-95% by weight of a compound of formula () or a mixture thereof. High concentrations can also be made that are intended for dilution before application. The carrier may be solid, liquid or aerosol. The actual composition may take the form of granules, powders, powders, solutions, emulsions, slurries, aerosols. Suitable solid carriers that can be used include, for example, natural clays (kaolin, attapulgite, montmorillonite, etc.), talc, pyrophyllite, diatomaceous silica, synthetic fine-grained silica, calcium aluminosilicate, calcium phosphate, and the like. Organic substances such as blackberry husk powder, cottonseed hulls, wheat flour, wood flour, and bark powder can also be used as carriers. Suitable liquid diluents include, for example, water, organic solvents (hydrocarbons such as benzene, toluene, dimethyl sulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like. Suitable aerosol carriers include conventional aerosol carriers such as halogenated ancanes. Various accelerators and surfactants that enhance the extent of transfer of active compounds into plant tissue, such as organic solvents, wetting agents and oils, and in the case of compositions intended for pre-emergence application, reduce the leachability of the compounds. Alternatively, agents that promote soil stability can be included in the composition. The compositions may also contain various adjuvants, stabilizers, conditioners, insecticides, fungicides and, if necessary, other herbicidal compounds. At low doses, the compounds of the invention exhibit plant growth regulating activity and can be used to alter the normal growth pattern of young plants. The compounds of formula () can be applied in pure form as plant growth regulators, but more practically in the case of herbicidal applications they are used together with carriers. The same types of carriers described above for herbicidal compositions can also be used. Depending on the intended application, the plant growth regulating composition can be combined with other compatible ingredients such as desiccant, defoliant, surfactant, adjuvant, fungicide, insecticide. Generally, plant growth regulating compositions, whether applied directly or in dilution, include:
Contains about 0.005 to 90% by weight of a compound of formula (). The invention can be further understood from the examples described below. Unless otherwise specified, temperatures are in degrees Celsius and room or ambient temperature is about 20-25°C. Percentages are by weight and moles are gram-moles. Equivalent means the equivalent molar amount of reagent to the moles of reactants described in the example for a given mole or weight or volume. Broton-magnetic resonance spectra (PMR or NMR) are measured at 60 mHz and the symbols are singlet (s), broad singlet (bs), doublet (d), double doublet (dd),
Triplet (t), double triplet (dt), quartet (q) and multiplet (m)
It is expressed as cps means cycles per second. Repeat if necessary to provide additional starting materials for subsequent examples. Example 1 (3-Trifluoromethylphenyl)-benzylcarbonyl-acetonitrile In this example, 4.91 g of metallic sodium was added to 110 ml of absolute ethanol at room temperature and stirred until all the sodium was dissolved. A mixture of 18.76 g (3-trifluoromethylphenyl)acetonitrile and 21.73 g ethyl phenyl acetate was added dropwise and the resulting mixture was stirred under reflux for about 18 hours. The mixture was then poured into 300 ml of water and extracted three times with ethyl ether. The pH of the extracted aqueous layer was adjusted to about 1 with 10% by weight hydrochloric acid, and the mixture was extracted again three times with ethyl ether. The organic layer was washed twice with saturated sodium bicarbonate solution, dried over magnesium sulfate and evaporated to dryness under vacuum to yield 22.6 g of the title compound. Similarly, the following compounds can be prepared using the procedures described above using appropriately substituted phenylacetonitrile and ethyl substituted phenylacetate starting materials. (5-chloro-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, (4-chloro-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, (2-bromo-3-trifluoromethylphenyl) )-benzylcarbonyl-acetonitrile, (6-fluoro-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, (4-methyl-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, (5-methoxy- 3-Trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, (6-methyl-3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile, (3,5-di-trifluoromethylphenyl)-
Benzylcarbonyl-acetonitrile, (3-difluoromethoxyphenyl)-benzylcarbonyl-acetonitrile, (3-trifluoromethoxyphenyl)-benzylcarbonyl-acetonitrile, (3-trifluoromethylphenyl)-(4-fluorobenzyl) carbonyl)-acetonitrile, (3-trifluoromethylphenyl)-1-naphthylmethylene-acetonitrile, (2-chloro-3-methylphenyl)-benzylcarbonyl-acetonitrile, (4-ethyl-3-methylphenyl)-benzylcarbonyl- Acetonitrile, (5-methoxy-3-fluorophenyl)-benzylcarbonyl-acetonitrile, (3-iodophenyl)-benzylcarbonyl-acetonitrile, (3-difluoromethylthiophenyl)-benzylcarbonyl-acetonitrile, (3-trifluoromethylthiophenyl) enyl)-benzylcarbonyl-acetonitrile, (3,5-diethoxyphenyl)-benzylcarbonyl-acetonitrile, (3-promophenyl)-(2-nitrobenzylcarbonyl)-acetonitrile, (2-chloro-3-methylphenyl)- Benzylcarbonyl-acetonitrile, (3-bromo-2-ethylphenyl)-naphthyl-1-methylenecarbonyl-acetonitrile, (2,3-dimethylphenyl)-β-naphthyl-1-methylcarbonyl-acetonitrile, (3-chlorophenyl) -benzylcarbonyl-acetonitrile, (3-methylphenyl)-benzylcarbonyl-acetonitrile, (3-t-butoxyphenyl)-benzylcarbonyl-acetonitrile, (3-bropylphenyl)-benzylcarbonyl-acetonitrile, (3-bromophenyl)-benzylcarbonyl- Acetonitrile, (3-iodophenyl)-(3-nitrobenzylcarbonyl)-acetonitrile, (3-trifluoromethylphenyl)-(2,3-
dichlorobenzylcarbonyl)-acetonitrile, (3-methoxyphenyl)-1-naphthyl-methylenecarbonyl-acetonitrile, (3-trifluoromethyl)-(3-chloro-8-
Fluoro-1-naphthyl-methylenecarbonyl)-
Acetonitrile, (3-trifluoromethyl)-[(2-trifluoromethyl-3-methyl-8-methoxy-1-naphthyl)methylenecarbonyl]-acetonitrile, (3-trifluoromethyl)-(1-indenyl-
methylenecarbonyl)-acetonitrile and (3-trifluoromethyl)-(2-fluoro-1-
indenyl-methylenecarbonyl)-acetonitrile. Example 2 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-
Dihydrofuran In this example, a solution of 21.8 g (3-trifluoromethylphenyl)-benzylcarbonyl-acetonitrile in 60 ml acetic acid was added dropwise to a solution of 12.65 g bromine in 20 ml glacial acetic acid. The reaction mixture was stirred at room temperature for about 16 hours. Pour the reaction mixture into 250ml of water,
The resulting mixture was extracted three times with ethyl ether. The organic extracts were washed with saturated sodium bicarbonate solution, dried over magnesium sulfate, and concentrated in vacuo to give a white solid.
8.4 g was obtained, and after dehydration, 7.0 g of the title compound was obtained. Similarly, applying the above procedure to the compound listed in Example 1, the following compound can be obtained. 2-phenyl-3-oxo-4-(5-chloro-3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(4-chloro- 3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethylphenyl)-5-amino-2, 3-dihydrofuran, 2-phenyl-3-oxo-4-(6-fluoro-3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4- (4-Methyl-3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethylphenyl)-5 -amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(6-methyl-3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3 -oxo-4-(3,5-di-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trihydrofuran) fluoromethoxyphenyl)-5-amino-2,3-
Dihydrofuran, 2-(4-fluorophenyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(3-
trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(2-chloro-3-methylphenyl)-5-amino-2,3-
Dihydrofuran, 2-phenyl-3-oxo-4-(4-ethyl-3-methylphenyl)-5-amino-2,3-
Dihydrofuran, 2-phenyl-3-oxo-4-(5-methoxy-3-chlorophenyl)-5-amino-2,3
-dihydrofuran, 2-phenyl-3-oxo-4-(3-indophenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-difluoromethylthiophenyl) -5-amino-2,3-
Dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-amino-2,3
-dihydrofuran, 2-phenyl-3-oxo-4-(3,5-diethoxyphenyl)-5-amino-2,3-dihydrofuran, 2-(2-nitrophenyl)-3-oxo-4-
(3-bromophenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(2-chloro-3-methylphenyl)-5-amino-2,3-
Dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(3-
Bromo-2-ethylphenyl)-5-amino-2,
3-dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(2,
3-dimethylphenyl)-5-amino-2,3-
Dihydrofuran, 2-phenyl-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-methylphenyl)-5-amino- 2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-butoxyphenyl)-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-propylphenyl )-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-bromophenyl)-5-amino-2,3-dihydrofuran, 2-(3-nitrophenyl)-3- Oxo-4-
(3-iodophenyl)-5-amino-2,3-dihydrofuran, 2-(2,3-difluorophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3 -dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(3-
methoxyphenyl)-5-amino-2,3-dihydrofuran, 2-(3-chloro-8-fluoro-1-naphthyl)
-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(2-trifluoromethyl-3-methyl-8
-methoxy-1-naphthyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-inden-1-yl-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran and 2-(2-fluoroinden-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5
-Amino-2,3-dihydrofuran. Example 3 2-Methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran Dry 500 ml 3-neck round fitted with mechanical stirrer, funnel and reflux condenser 100 ml of ethanol was introduced into the bottom flask. While stirring the solvent, 3.5 g of sodium was added. After dissolving all the metals, add ethyl L in 30ml ethanol.
A solution of 13.0 g of -(+)-lactate and 18.5 g of m-trifluoromethylphenylacetonitrile was added to the reaction mixture. After the mixture turned dark red and the addition was complete, the mixture was heated at reflux overnight (approximately 18 hours). The mixture was then cooled to room temperature and diluted with 300 ml of water.
ml and the product mixture was acidified (PH ca. 1) with 10% hydrochloric acid. The mixture was extracted with ether (3 times) and the organic extracts were diluted with saturated sodium bicarbonate solution.
Washed twice, dried over magnesium sulfate, and concentrated in vacuo to give a thick oil. This oil was taken up in an ether/petroleum ether mixture, and the desired compound crystallized out as a yellow powder. Two crystals were collected, yielding 4.7 g of the title compound. Similarly, the following compounds can be prepared by the above procedure using appropriately substituted starting materials. 2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-ethyl-3-oxo-4-(5-chloro-
3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-cyclopentyl-3-oxo-4-(3-
trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-vinyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-allyl-3-oxo-4-(3-trifluoromethylphenyl) fluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-allyl-3-oxo-4-(2-methoxy-3-trifluoromethylphenyl)-5-amino-2,3-dihydro Furan, 2-trifluoromethyl-3-oxo-4-(3
-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-methyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-amino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-trihydrofuran) fluoromethoxyphenyl)-5-amino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(5-propoxy-3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-amino-2 ,3-
Dihydrofuran, 2-ethyl-3-oxo-4-(2-chloro-
3-fluorophenyl)-5-amino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3-methyl-
4-methoxyphenyl)-5-amino-2,3-
Dihydrofuran, 2-allyl-3-oxo-4-(3,6-dimethylphenyl)-5-amino-2,3-dihydrofuran, 2-trifluoromethyl-3-oxo-4-(3
-trifluoromethyl-4-bromophenyl)-5
-amino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(3-nitro-4-methylphenyl)-5-amino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-methoxyphenyl)-5-amino-2,3-dihydrofuran, 2-Methyl-3-oxo-4-(3-difluoromethylthiophenyl)-5-amino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-trifluoromethylthiophenyl) -5-amino-2,3-
Dihydrofuran, 2-ethyl-3-oxo-4-(3-chlorophenyl)-5-amino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3-methylphenyl)-5-amino- 2,3-dihydrofuran, 2-allyl-3-oxo-4-[3,5-di(trifluoromethyl)-phenyl]-5-amino-
2,3-dihydrofuran, 2-trifluoromethyl-3-oxo-4-(4
-fluorophenyl)-5-amino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(2-bromophenyl)-3-oxo-5-amino-2,3-dihydrofuran, 2-propyl-3-oxo-4-(2-methoxy-3-fluorophenyl)-5-amino-2,3
-dihydrofuran, 2-butyl-3-oxo-4-(2-chloro-
3-fluorophenyl)-5-amino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3-chloro-
4-methoxyphenyl)-5-amino-2,3-
Dihydrofuran, 2-allyl-3-oxo-4-(3,5-dimethylphenyl)-5-amino-2,3-dihydrofuran, 2-(trifluoromethyl)-3-oxo-4-
(3-trifluoromethyl-5-bromophenyl)-
5-amino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(3-Fluoro-4-methylphenyl)-3-oxo-5-amino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-methoxyphenyl)-5-amino-2,3 -dihydrofuran, 2-methyl-3-oxo-4-(3,5-difluorophenyl)-5-amino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3,5-diethylphenyl) enyl)-5-amino-2,3-dihydrofuran, 2-allyl-3-oxo-4-(3-proboxyphenyl)-5-amino-2,3-dihydrofuran, 2-trifluoromethyl- 3-oxo-4-(3
-fluorophenyl)-5-amino-2,3-dihydrofuran, 2-propyl-3-oxo-4-(3-bromophenyl)-3-oxo-5-amino-2,3-
Dihydrofuran, 2-phenyl-3-oxo-4-(2-iodo-3-fluorophenyl)-5-amino-2,3-
Dihydrofuran, 2-benzyl-3-oxo-4-(2-isopropoxy-3-trifluoromethylphenyl)-5
-Amino-2,3-dihydrofuran, 2-(3-chlorophenyl)-3-oxo-4-
(2,3-dimethylphenyl)-5-amino-2,
3-dihydrofuran, 2-naphthyl-1,3-oxo-4-(3-trifluoromethyl-4-bromophenyl)-5-amino-2,3-dihydrofuran, 2-(3-methylphenyl)-3- Oxo-4-
(3-Butyl-4-methylphenyl)-3-oxo-5-amino-2,3-dihydrofuran, 2-(3-chlorophenyl)-3-oxo-4-
(3-chlorophenyl)-5-amino-2,3-dihydrofuran, 2-(2,3,5-trifluorophenyl)-3-
Oxo-4-(3-trifluoromethylphenyl)-
5-amino-2,3-dihydrofuran, 2-(3-methylnaphthyl-1)-3-oxo-
4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(di-chlorovinyl-3-oxo-4-(3
-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-fluoromethyl-3-oxo-4-(3-
trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-methoxymethylene-3-oxo-4-(3
-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-propoxymethylene-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-ethoxymethylene-3-oxo-4-(3
-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-(2-methoxypropyl)-3-oxo-4
-(3-trifluoromethylphenyl), 5-amino-2,3-dihydrofuran, 2-methylthiomethylene-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran and 2-(1-propylthioethyl)-3-oxo-
4-(3-Trifluoromethylphenyl)-5-amino-2,3-dihydrofuran Example 4 (3-trifluoromethylphenyl)-methoxyacetyl-acetonitrile In this example, 5.6 g of sodium metal was added under a nitrogen atmosphere. The mixture was added to 120 ml of absolute ethanol using nitrogen water to release hydrogen. After the hydrogen evolution is complete, add 30 g of (3-trifluoromethylphenyl)-acetonitrile and methylmethoxyacetate in absolute ethanol.
18.5 g of the mixture was added and the resulting mixture was refluxed for 3-4 hours. The mixture was added to 300 ml of water and extracted three times with petroleum ether. The remaining aqueous phase is brought to approximately PH with 10% hydrochloric acid.
1 and extracted three times with ethyl ether.
The ethyl ether extracts were combined, washed twice with saturated sodium bicarbonate solution, dried over magnesium sulphate and concentrated by evaporation. The concentrate was evaporated under vacuum to give an oil which was triturated with ethyl ether.
The mixture was then filtered to remove the solids and the filtrate was evaporated in vacuo to yield 36.9 g of the title compound as a brown solid. Similarly, (3-trifluoromethylphenyl)
Corresponding substituted and disubstituted phenyl related compounds can be prepared using the above method, but using other (substituted and disubstituted phenyl) acetonitrile in place of acetonitrile. Example 5 (3-trifluoromethylphenyl)-2-methoxyisovaleryl-acetonitrile In this example, (3-trifluoromethylphenyl)
10 g of -methoxyacetyl-acetonitrile was added dropwise to a slurry of 1.87 g of sodium hydride in 20 ml of tetrahydrofuran at about 0 DEG C. under a nitrogen atmosphere to release hydrogen. After no hydrogen evolution was observed, the mixture was cooled to approximately −78°C and dissolved in hexane.
24.3 ml of 1.6Mn-butyllithium was added dropwise. The mixture was stirred at -78°C for 1.5 hours and then at about 0-4°C.
Stir for 20 minutes. After this, 2-iodopropane
3.9 ml (approximately 6.64 g) was added dropwise and the mixture was stirred overnight (approximately 14-16 hours). Then add the mixture to water and
Acidified with 10% hydrochloric acid and extracted three times with ethyl ether. The extracts were combined, dried over magnesium sulfate and concentrated in vacuo to give 11.4 g of the title compound as an oil. Similarly, the following compounds can be prepared by the same procedure, but using the appropriate alkyl, aryl or substituted aryl, iodo, bromide or chloride in place of iodopropane. (3-Trifluoromethylphenyl)-(2-methoxy-3-phenylpropionyl)-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-(2-fluorophenyl)propionyl]
-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-(3-methylphenyl)propionyl]
-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-(2-ethoxyphenyl)propionyl]-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-( 3-nitrophenyl)propionyl)
-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-(2-trifluoromethylphenyl)-propionyl]-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy- 3-(2-chloro-3-propylphenyl)
propionyl]-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-(2-nitro-3-methoxyphenyl)
propionyl]-acetonitrile, (3-trifluoromethylphenyl)-[2-methoxy-3-(2-fluoro-3-2'-2'-difluoroethyl phenyl)propionyl]-acetonitrile, (3-trifluoromethylphenyl) Fluoromethylphenyl)-[2-methoxy-3-(2,3-dichloro-6-methylphenyl)propionyl]acetonitrile, (3-trifluoromethylphenyl)-(2-methoxy-4-phenylbutyryl)-acetonitrile, (3-Trifluoromethylphenyl)-[2-methoxy-5-(2-bromophenyl)valeryl]-acetonitrile, (3-trifluoromethylphenyl)-(2-methoxy-3-methyl-4-phenylbutyryl) -acetonitrile, (3-trifluoromethyl)-(2-methoxy-3
-naphth-1-ylpropionyl)-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(2-fluoronaphth-1-yl)propionyl]
-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(3-butylnaphth-1-yl)propionyl]
-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(5-methoxynaphth-1-yl)propionyl]-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(6-nitronaphth-1-yl)propionyl]
-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(7-trifluoromethylnaphth-1-yl)propionyl]-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(2-chloro-8-methylnaphth-1-yl)
propionyl]-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-(3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl)propionyl]-acetonitrile, (3-trifluoromethyl)-(2-methoxy-4
-naphth-1-ylbutyryl)-acetonitrile, (3-trifluoromethyl)-[2-methoxy-5
-(8-fluoronaphth-1-yl)valeryl]-acetonitrile, (3-trifluoromethyl)-[2-methoxy-3
-Methyl-3-(7-methoxynaphth-1-yl)
propionyl]-acetonitrile, (3-trifluoromethylphenyl)-(2-methoxy-3-inden-1-ylpropionyl)-
Acetonitrile and (3-trifluoromethylphenyl)-[2-methoxy-3-(2-fluoroinden-1-yl)propionyl]-acetonitrile. Similarly, (3-trifluoromethylphenyl)-
The corresponding mono- or di-substituted phenyl derivatives of the above compounds are prepared by carrying out the above method using other (mono- or disubstituted phenyl)-(methoxyacetyl)-acetonitrile in place of (2-methoxyacetyl)-acetonitrile. can do. Example 6 2-isopropyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran In this example, (3-trifluoromethylphenyl)
-(2-methoxyisovaleryl)-acetonitrile
A mixture of 11.4 g and 7.8 g of concentrated sulfuric acid in 50 ml of acetic acid was refluxed for 30 minutes.
Warmed for minutes and evaporated under vacuum. The concentrate was mixed with diethyl ether, washed three times with 1N sodium hydroxide, dried over magnesium sulfate, and evaporated to give an oil. 20% oil (by volume)
Ethyl acetate: Mix in 80% petroleum ether overnight (14
~16 hours). The solids were collected by filtration and washed three times with 20% (by volume) ethyl acetate:80% petroleum ether.
2.9 g of the title compound was obtained. Similarly, the following compounds can be prepared by carrying out the above procedure using 3-trifluoromethylphenyl-dimethoxyacetyl-acetonitrile, which can be prepared by the method of Example 1, and the other compounds described in Example 5. 2-methoxy-3-oxo-4-(3-trifluoromethylphenyl-5-amino-2,3-dihydrofuran, 2-benzyl-3-oxo-4-(3-trifluoromethylphenyl)- 5-Amino-2,3-dihydrofuran, 2-(2-fluorobenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-(3-methylbenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran 2-(2-ethoxybenzyl)-3-oxo-4
-(3-trifluoromethylpheny)yl-5-amino-2,3-dihydrofuran, 2-(3-nitrobenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-(4-fluorobenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-amino-
2,3-dihydrofuran, 2-(2-trifluoromethylbenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5
-amino-2,3-dihydrofuran, 2-(2-chloro-3-propylphenyl)-3
-oxo-4-(3-trifluoromethylphenyl)
-5-amino-2,3-dihydrofuran, 2-(2-nitro-3-methoxyphenyl)-3
-oxo-4-(3-trifluoromethylphenyl-5-amino-2,3-dihydrofuran, 2-(2-fluoro-3-2',2'-dichloroethylbenzyl)-3-oxo-4 -(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(2,3-dichloro-6-methylbenzyl)
-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran 2-(β-phenethyl)-3-oxo-4-(3
-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-[3-(2-bromophenyl)propyl]-
3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-[1-methyl-2-(phenyl)ethyl]-
3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-naphth-1-ylmethylene-3-oxo-
4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(2-fluoronaphth-1-ylmethylene)-
3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(3-butylnaphth-1-ylmethylene)-
3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(5-methoxynaphth-1-ylmethylene)
-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(6-nitronaphth-1-ylmethylene)-
3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(7-trifluoromethylnaphth-1-ylmethylene)-3-oxo-4-(3 -trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2-(2-chloro-8-methylnaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran, 2-(3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl)-3-oxo-4-(3
-trifluoromethylphenyl)-5-amino-2,
3-dihydrofuran, 2-(β-naphth-1-ylethyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-
Amino-2,3-dihydrofuran, 2-[β-(8-fluoronaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3- Dihydrofuran, 2-[1-(7-methoxynaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, 2- inden-1-ylmethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran, and 2-(2-fluoroinden-1-ylmethylene)
-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran. Similarly, the above process is carried out using the corresponding mono- and di-substituted compounds of the starting materials of the above compounds and the corresponding 4-(3-methylphenyl); 4-(3-β-fluoroethoxyphenyl) ; 4-(3-difluoromethylenethiophenyl); 4-(3-chlorophenyl); 4-(2-bromo-3-trifluoromethylphenyl)- and 4
-(2-Methyl-3-difluoromethylenethiophenyl compound can be produced. Example 7 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2 ，
3-Dihydrofuran In this example, approximately 1 g of solid sodium hydroxide in 4.0 ml of water is dissolved in 2-dihydrofuran in 50 ml of methylene chloride at room temperature.
Add to 3 g of phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran mixture, then add 1.19 g of dimethyl sulfate and 0.21 g of benzyltriethylammonium chloride. Ta. The resulting two-phase mixture was stirred at room temperature for about 2 hours, washed three times with water, dried over magnesium sulfate, and then concentrated under vacuum. The residue was purified by chromatography on silica gel eluting with a mixture of tetrahydrofuran and chloroform to give the title compound. Similarly, the corresponding 5-methylamino compounds can be prepared by carrying out the process described above using the products listed in Examples 2, 3 and 6 as starting materials. For example, 2-phenyl-3-oxo-4-(5-chloro-3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(4 -Chloro-3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethylphenyl)-5- Methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(6-chloro-3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl- 3-oxo-4-(4-methyl-3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(5-methoxy-3-trihydrofuran) fluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(6-methyl-3-trifluoromethylphenyl)-5-methylamino-2,3 -dihydrofuran, 2-phenyl-3-oxo-4-(3,5-di-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4- (3-difluoromethoxyphenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-methylamino-
2,3-dihydrofuran, 2-(4-fluorophenyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(3-
trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(2-chloro-3-methylphenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(4-ethyl-3-methylphenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(5-methoxy-3-chlorophenyl)-5-methylamino-
2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-indophenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-difluoro methylthiophenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-methylamino-
2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3,5-diethoxyphenyl)-5-methylamino-2,3
-dihydrofuran, 2-(2-nitrophenyl)-3-oxo-4-
(3-bromophenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(2-chloro-3-methylphenyl)-5-methylamino-2,
3-dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(3-
Bromo-2-ethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(1-naphthyl)-3-oxo-4-(2,
3-dimethylphenyl)-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-methylphenyl)-5 -Methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-butoxyphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-( 2-propylphenyl)-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-bromophenyl)-5-methylamino-2,3-dihydrofuran, 2-( 3-nitrophenyl)-3-oxo-4-
(3-iodophenyl)-5-methylamino-2,
3-dihydrofuran, 2-(2,3-dichlorobenzyl)-3-oxo-4-(2-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(1-naphthyl) )-3-oxo-4-(3-
methoxyphenyl)-5-methylamino-2,3
-dihydrofuran, 2-(3-chloro-8-fluoronaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2- (2-trifluoromethyl-3-methyl-8
-methoxynaphth-1-yl)-3-oxo-4
-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-inden-1-yl-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(2-fluoroinden-1-yl)-3-oxo-4-(3-trifluoromethylphenyl) -5
-Methylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3
-dihydrofuran, 2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3
-dihydrofuran, 2-ethyl-3-oxo-4-(5-chloro-
3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-cyclopentyl-3-oxo-4-(3-
trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3
-dihydrofuran, 2-allyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3
-dihydrofuran, 2-allyl-3-oxo-4-(2-methoxy-3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-trifluoromethyl-3-oxo- 4-(3
-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-difluoromethoxyphenyl)-5-methylamino-2,3
-dihydrofuran, 2-methyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-methylamino-2,
3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(5-nitro-3-trifluoromethylphenyl)-
5-methylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-methylamino-2,
3-dihydrofuran, 2-ethyl-3-oxo-4-(2-chloro-
3-chlorophenyl)-5-methylamino-2,
3-dihydrofuran, 2-vinyl-3-oxo-4-(3-methyl-
4-methoxyphenyl)-5-methylamino-2,
3-dihydrofuran, 2-allyl-3-oxo-4-(3,6-dimethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-trifluoromethyl-3-oxo-4-( 3
-trifluoromethyl-4-bromophenyl)-5
-methylamino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(3-nitro-4-methylphenyl)-3-oxo-5-methylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-methoxyphenyl)-5-methylamino-2 ,3-dihydrofuran, 2-methyl-3-oxo-4-(3-dichloromethylthiophenyl)-5-methylamino-2,
3-dihydrofuran, 2-methyl-3-oxo-4-(3-trifluoromethylthiophenyl)-5-methylamino-2,
3-dihydrofuran, 2-ethyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3-methylphenyl)-5 -Methylamino-2,3-dihydrofuran, 2-allyl-3-oxo-4-[3,5-di(trifluoromethyl)phenyl]-5-methylamino-2,3-dihydrofuran, 2-tri Fluoromethyl-3-oxo-4-(4
-fluorophenyl)-5-methylamino-2,3
-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(2-bromophenyl)-3-oxo-5-methylamino-2,3-dihydrofuran 2-propyl-3-oxo-4-(2-methoxy-3-chlorophenyl)-5-methylamino-
2,3-dihydrofuran, 2-butyl-3-oxo-4-(2-chloro-
3-fluorophenyl)-5-methylamino-2,
3-dihydrofuran, 2-vinyl-3-oxo-4-(3-chloro-
4-methoxyphenyl)-5-methylamino-2,
3-dihydrofuran, 2-allyl-3-oxo-4-(3,6-dimethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-trichloromethyl-3-oxo-4-(3
-trichloromethyl-5-bromophenyl)-5
-methylamino-2,3-dihydrofuran, 2-(2-chlorovinyl)-3-oxo-4-
(3-chloro-4-methylphenyl)-3-oxo-5-methylamino-2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-methoxyphenyl)-5-methylamino-2 ,3-dihydrofuran, 2-methyl-3-oxo-4-(3,5-difluorophenyl)-5-methylamino-2,3-dihydrofuran, 2-vinyl-3-oxo-4-(3,5 -diethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-allyl-3-oxo-4-(3-propoxyphenyl)-5-methylamino-2,3-dihydrofuran, 2- Trichloromethyl-3-oxo-4-(3
-fluorophenyl)-5-methylamino-2,3
-dihydrofuran, 2-propyl-3-oxo-4-(2-bromophenyl)-3-oxo-5-methylamino-2,
3-dihydrofuran, 2-phenyl-3-oxo-4-(2-iodo-3-fluorophenyl)-5-methylamino-2,
3-dihydrofuran, 2-benzyl-3-oxo-4-(2-isopropoxy-3-trifluoromethylphenyl)-5
-methylamino-2,3-dihydrofuran, 2-(3-chlorophenyl)-3-oxo-4-
(2,3-dimethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-naphth-1-yl-3-oxo-4-(3
-trichloromethyl-4-bromophenyl)-5
-Methylamino-2,3-dihydrofuran, 2-(3-methylphenyl)-3-oxo-4-
(3-Butyl-4-methylphenyl)-3-oxo-5-methylamino-2,3-dihydrofuran, 2-(3-fluorophenyl)-3-oxo-4-
(3-chlorophenyl)-5-methylamino-2,
3-dihydrofuran, 2-(2,3,5-trifluorophenyl)-3-
Oxo-4-(trifluoromethylphenyl)-5-
Methylamino-2,3-dihydrofuran, 2-(3-methylnaphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-
Methylamino-2,3-dihydrofuran, 2-(1'-chlorovinyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-fluoromethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-
2,3-dihydrofuran, 2-methoxymethylene-3-oxo-4-(3
-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-propoxymethylene-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-ethoxymethylene-3-oxo-4-(3
-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(2-methoxypropyl)-3-oxo-4
-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-methylthiomethylene-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(1-propylthioethyl)-3-oxo-
4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-benzyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2 ，
3-dihydrofuran, 2-(2-fluorobenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(3-methylbenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(2-ethoxybenzyl)-3-oxo-4
-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(3-etrobenzyl)-3-oxo-4-
(3-Trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran 2-(4-fluorobenzyl)-3-oxo-4-
(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(2-trifluoromethylbenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5 −
Methylamino-2,3-dihydrofuran, 2-(chloro-3-propylphenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5
-methylamino-2,3-dihydrofuran, 2-(2-nitro-3-methoxyphenyl)-3
-oxo-4-(3-trifluoromethylphenyl)
-5-methylamino-2,3-dihydrofuran, 2-(2-chloro-3-2',2'-dichloroethylbenzyl)-3-oxo-4-(3-trifluoromethylphenyl)-5 -methylamino-2,3-
Dihydrofuran, 2-(2,3-dichloro-6-methylbenzyl)
-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(β-phenethyl)-3-oxo-4-(3
-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-[3-(2-bromophenyl)propyl]-
3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-[1-methyl-2-(phenyl)ethyl]-
3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-naphth-1-ylmethylene-3-oxo-
4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(2-fluoronaphth-1-ylmethylene)-
3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(3-butylnaphth-1-ylmethylene)-
3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(5-methoxynaphth-1-ylmethylene)
-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(6-nitronaphth-1-ylmethylene)-
3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-(7-trifluoromethylnaphth-1-ylmethylene)-3-oxo-4-( 3-trifluoromethylphenyl)-5-methylamino-2,3-difluorofuran, 2-(2-chloro-8-methylnaphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl )-5-methylamino-2,3-
Dihydrofuran, 2-(3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl)-3-oxo-4-(3
-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran, 2-methoxy-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,
3-dihydrofuran, 2-(β-naphth-1-ylethyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-
Methylamino-2,3-dihydrofuran, 2-[β-(8-fluoronaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2, 3-dihydrofuran, 2-[1-(7-methoxynaphth-1-yl)ethyl]-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran , 2-inden-1-ylmethylene-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran and 2-(2-fluoroinden-1-ylmethylene)
-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,3-dihydrofuran. Similarly, approximately double the amount of dimethyl sulfate,
The corresponding 5-dimethylamino compound of the above compound can be prepared by increasing the reaction time. Furthermore, 5-ethylamino and 5-diethylamino compounds corresponding to the above compounds can be produced by using diethyl sulfate in place of dimethyl sulfate. Example 8 2-(2-fluorophenyl)-3-oxo-4-
(3-Trifluoromethylphenyl)-5-allylamino-2,3-dihydrofuran Add 1 g of sodium hydroxide in 4.0 ml of water to 2-(2
-fluorophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-
A mixture of 4.0 g of dihydrofuran and 80 ml of methylene chloride was added, followed by 1.44 g of allyl bromide and 0.27 g of benzyltriethylammonium chloride. The resulting two-phase mixture was stirred at room temperature for about 18 hours, then washed three times with water, dried over magnesium sulfate, and concentrated under vacuum. The residue was purified by chromatography on silica gel eluting with chloroform to give 2.5 g of the title compound. Similarly, this method can be applied to the products listed in Examples 2, 3 and 6 to prepare the corresponding 5-allylamino compounds. Furthermore, the corresponding 5-diallylamino compound can be produced by approximately doubling the amounts of allyl bromide and sodium hydroxide. In this way, the corresponding 5-ethylamino and 5-diethylamino compounds can be prepared using ethyl bromide in place of allyl bromide. Similarly, instead of alkyl bromide, methoxymethyl bromide, ethylthiomethyl bromide, methyl bromoacetate, methyl 2-bromobutyrate, 1,5-dibromopentane and cis-1,4-dibromobuta-1,3-diene are used. Using the same method, the corresponding 5-methoxymethylamino, 5-ethylthiomethylamino, 5-methoxycarbonylmethylamino, 5-(1-methoxycarbonylpropyl) products listed in Examples 2, 3 and 6, respectively amino), 5-piperidine-
1-yl and 5-pyrrol-1-yl compounds can be produced. For example, 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxymethylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxymethylamino-2,3-dihydrofuran, methylphenyl)-5-methoxymethylamino-2,3-dihydrofuran, 2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxymethylamino-2,3-dihydrofuran , 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3-dihydrofuran, 2-methoxy-3-oxo-4-(3-trifluoromethylphenyl) methylphenyl)-5-ethylthiomethylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3- Dihydrofuran, 2-ethoxymethylene-3-oxo-4-(3
-trifluoromethylphenyl)-5-ethylthiomethylamino-2,3-dihydrofuran, 2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-ethylthiomethylamino-2 ,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrofuran, 2-methyl-3-oxo-4- (3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrofuran, 2-methylthiomethylene-3-oxo-4-
(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino-2,3-dihydrofuran, 2-ethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methoxycarbonylmethylamino -2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3-dihydrofuran, 2-Methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3-dihydrofuran, 2-fluoro-3-oxo- 4-(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3-dihydrofuran, 2-ethyl-3-oxo-4-(3-trifluoromethyl phenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3-dihydrofuran, 2-naphth-1-yl-3-oxo-4-(3
-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-2,3
-dihydrofuran, 2-inden-1-yl-3-oxo-4-
(3-trifluoromethylphenyl)-5-(1-methoxycarbonylprop-1-yl)amino-
2,3-dihydrofuran, 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-piperidin-1-yl-2,3-dihydrofuran and 2-phenyl-3-oxo- 4-(3-trifluoromethylphenyl)-5-pyrrol-1-yl-2,3-dihydrofuran. Similarly, the above method was carried out using the 5-methylamino compound of Example 7 as starting material and the corresponding 5-methylamino compound
-(N-methyl-N-allylamino), 5-(N-
Methyl-N-ethylamino), 5-(N-methyl-
N-methoxymethylamino), 5-(N-methyl-
N-ethylthiomethylamino), 5-(N-methyl-N-methoxycarbonylmethylamino) and 5-(N-methyl-N-1'-methoxycarbonylpropylamino) compounds can be produced. Example 9 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-2,
Lithium salt of 3-dihydrofuran (R ¹ =-
CH ₃ , R ² = Li) In this example, 5.4 ml of 1.6Mn-butyllithium in hexane was dissolved in 25 ml of tetrahydrofuran at -30°C.
A solution containing 2.86 g of -phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-2,3-dihydrofuran was added dropwise with stirring.
The resulting mixture was stirred for 20 minutes and concentrated under vacuum to yield 2.8 g of the title compound as a light brown solid. Analytical values: Calculated values C-63.74, H-3.84, N-4.13. Actual measurement value C-
61.82, H-4.90, N-3.48. Similarly, the corresponding lithium salts of the compounds of Examples 2-5 can be prepared using the above method. Example 10 The compounds listed in Table A below were prepared using appropriate starting materials and appropriate methods as described in the previous examples.

【table】

【table】

【table】

【table】

【table】

TABLE EXAMPLE 8 In this example, the compounds of Table A were tested for pre- and post-emergence activity against various weeds and broad-leaved plants, including cereal grasses and broad-leaved crops, using the methods described below. Test compounds are identified by compound number in Table A. Pre-emergence herbicidal test The pre-emergent herbicidal activity was measured as follows. Test solutions for each compound were prepared as follows. 355.5 mg of test compound was dissolved in 15 ml of acetone.
Acetone 2 containing 110 mg of nonionic surfactant
ml was added to the solution. 12ml of this stock solution
was added to 47.7 ml of water containing the same nonionic surfactant at a concentration of 625 mg/l. Seeds of the test plants were planted in soil in pots and the test solution was uniformly spread over the soil surface in an amount of 27.5 micrograms/cm ² or, in some cases, in the amounts shown in Table 1 below. Certain compounds were tested at doses as low as 15.6 micrograms/cm ² . The pots were watered and placed in a greenhouse.
The pots were watered periodically and the germination status and condition of germinated seedlings were observed for 3 weeks. At the end of this period, the herbicidal efficacy of the compounds was evaluated by physiological observation. 0~
A scale of 100 is used, with 0 indicating no plant toxicity and 100 indicating complete death. The test results are shown in Table 1. Post-emergence herbicidal test Test compounds were formulated in the same manner as in the pre-emergence test.
27.5 micrograms/ ^cm2 in plants 2 to 3 inches tall (wild oats, 3 to 4 inches tall,
(excluding soybeans and watergrass), 2
Two similar pots were evenly distributed with this formulation.
Once the plants were present, they were placed in a greenhouse and the roots were watered periodically as needed. Phytotoxic effects were observed regularly to determine ecological response to treatments. 3 weeks later,
The herbicidal effects of the compounds were evaluated based on these observations. A scale of 0 to 100 is used, with 0 indicating no phytotoxicity and 100 indicating complete death. The test results are shown in Table 2.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] As can be seen from Table 1, the compounds of the present invention generally exhibit excellent broad-spectrum effects on pre-emergence phytotoxic activity, especially compounds 2, 4, 7, 9, 12, 14, 16, 22.
That was the case. Furthermore, Table 2 shows that the present compounds exhibit post-emergence phytotoxic activity against broad-leaved plants and, in some cases, weeds, especially compounds 7, 9, 12, 14, 16,
22 and 23 are good. It can be seen that the comparative compounds are far inferior to the corresponding compounds of the present invention.

Claims (1)

[Claims] 1. General formula (wherein R is lower alkyl, cycloalkyl having 3 to 7 carbon atoms; lower alkenyl; 1 to 4 carbon atoms and 1 to 4 halo atoms independently selected from the group of fluorine, chlorine, bromine or iodine; haloalkyl having 3; 2 to 4 carbon atoms and fluorine;
1 independently selected from the group of chlorine, bromine or iodine
haloalkenyl having ~3 halo atoms; lower alkoxyalkyl having the alkyl and alkoxy moieties independently having 1 to 3 carbon atoms; alkylthioalkyl having the alkyl moiety independently having 1 to 3 carbon atoms phenyl, 1-naphthyl, 1-indenyl; 4-fluorophenyl; arylalkylene in which the alkylene moiety has 1 to 3 carbon atoms and the aryl moiety is phenyl, 1-naphthyl or 1-indenyl; or R
is the expression or (In the formula, 1 of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ ,
2 or 3 are independently selected from lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 to 3 carbon atoms and having 1 to 3 same or different halo atoms and the remainder are hydrogen and R ³ is a single bond or alkylene having 1 to 3 carbon atoms); R ¹ is hydrogen or a substituted arylalkyl having 1 to 4 carbon atoms; R ² is hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl; R ¹ and R ² together with adjacent nitrogen atoms form a saturated or unsaturated nitrogen heterocycle having 3 to 6 carbon atoms, one of which is a nitrogen atom and the rest are carbon atoms; X is hydrogen; halogen or trifluoromethyl, and can take any position on the phenyl ring; and Y is lower alkyl, lower alkoxy, halo, 1
lower haloalkyl having ~4 carbon atoms and having 1 to 3 identical or different halogen atoms,
lower haloalkoxy having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms,
or lower haloalkylthio having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms, provided that when Y is halogen, R,
R ¹ and R ² are not all hydrogen, Y is other than trifluoromethyl, X is other than hydrogen, and R ¹ and R ² are each hydrogen, R is methyl,
and compatible salts thereof. 2. A compound according to claim 1, wherein one of R ¹ or R ² is hydrogen, methyl, ethyl or propyl. 3 One of R ¹ or R ² is methyl or ethyl,
2. A compound according to claim 1, wherein the other is hydrogen, methyl or ethyl. 4 One of R ¹ or R ² is hydrogen, the other is methyl,
2. A compound according to claim 1, which is ethyl or propyl. 5. A compound according to claim 1, wherein 5X is hydrogen. 3. A compound according to claim 2, wherein 6X is hydrogen. 7. A compound according to claim 3, wherein X is hydrogen. 8. A compound according to claim 1, wherein R is phenyl, 1-naphthyl, 4-fluorophenyl or substituted aryl. 9. A compound according to claim 8, wherein 9R is phenyl, naphthyl or monosubstituted phenyl. 10. A compound according to claim 9, wherein 10R is phenyl, halophenyl or lower alkyl phenyl. 11 R is phenyl, 4-fluorophenyl, 2-
11. The compound according to claim 10, which is halofenyl or 2-lower alkyl phenyl. 12 X is hydrogen, R ¹ and R ² are independently hydrogen,
Claim 11 selected from the group of methyl or ethyl.
Compounds described. 2. A compound according to claim 1, wherein 13 R is lower alkyl, cycloalkyl, lower alkenyl, haloalkyl or haloalkenyl. 14. A compound according to claim 13, wherein one of 14 R ¹ or R ² is hydrogen, methyl or ethyl and the other is methyl or ethyl. 15 R is methyl, ethyl or propyl,
15. A compound according to claim 14. 16. A compound according to claim 15, wherein one of 16 R ¹ or R ² is hydrogen and the other is methyl or ethyl. 17. The compound of claim 16, wherein 17X is hydrogen. 2. A compound according to claim 1, wherein 18Y is trifluoromethyl. 19. A compound according to claim 18, wherein R ¹ and R ² are independently hydrogen, methyl or ethyl. 19. A compound according to claim 18, wherein one of 20 R ¹ or R ² is methyl or ethyl and the other is hydrogen. 19. The compound of claim 18, wherein 21R is lower alkyl, cycloalkyl, lower alkenyl, lower haloalkyl or lower haloalkenyl. 19. The compound of claim 18, wherein 22X is hydrogen. 23 General formula (wherein R is lower alkyl, cycloalkyl having 3 to 7 carbon atoms; lower alkenyl; 1 to 4 carbon atoms and 1 to 4 halo atoms independently selected from the group of fluorine, chlorine, bromine or iodine; haloalkyl having 3; 2 to 4 carbon atoms and fluorine;
1 independently selected from the group of chlorine, bromine or iodine
haloalkenyl having ~3 halo atoms; lower alkoxyalkyl having the alkyl and alkoxy moieties independently having 1 to 3 carbon atoms; alkylthioalkyl having the alkyl moiety independently having 1 to 3 carbon atoms phenyl, 1-naphthyl, 1-indenyl; 4-fluorophenyl; arylalkylene in which the alkylene moiety has 1 to 3 carbon atoms and the aryl moiety is phenyl, 1-naphthyl or 1-indenyl; or R
is the expression or (In the formula, 1 of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ ,
2 or 3 are independently selected from lower alkyl, lower alkoxy, halo, nitro or haloalkyl having 1 to 3 carbon atoms and having 1 to 3 same or different halo atoms and the remainder are hydrogen and R ³ is a single bond or alkylene having 1 to 3 carbon atoms; R ¹ is hydrogen or substituted arylalkyl having 1 to 4 carbon atoms; alkyl; R ² is hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl; R ¹ and R ² together with adjacent nitrogen atoms form a saturated or unsaturated nitrogen heterocycle having 3 to 6 carbon atoms (one of which is a nitrogen atom and the rest are carbon atoms); X is hydrogen, halogen , or trifluoromethyl, and can take any position on the phenyl ring; and Y is lower alkyl, lower alkoxy, halo, 1
lower haloalkyl having ~4 carbon atoms and having 1 to 3 identical or different halogen atoms,
lower haloalkoxy having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms,
or lower haloalkylthio having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms, provided that when Y is halogen, R,
R ¹ and R ² are not all hydrogen, Y is other than trifluoromethyl, X is other than hydrogen, and R ¹ and R ² are each hydrogen, R is methyl,
1. A herbicidal composition comprising a herbicidally effective amount of a compound having ethyl, propyl, 2-halophenyl, 2-lower alkyl phenyl or 4-fluorophenyl, and a miscible carrier. 24 General formula (wherein R is lower alkyl, cycloalkyl having 3 to 7 carbon atoms; lower alkenyl; 1 to 4 carbon atoms and 1 to 4 halo atoms independently selected from the group of fluorine, chlorine, bromine or iodine; haloalkyl having 3; 2 to 4 carbon atoms and fluorine;
1 independently selected from the group of chlorine, bromine or iodine
haloalkenyl having ~3 halo atoms; lower alkoxyalkyl having the alkyl and alkoxy moieties independently having 1 to 3 carbon atoms; alkylthioalkyl having the alkyl moiety independently having 1 to 3 carbon atoms phenyl, 1-naphthyl, 1-indenyl; 4-fluorophenyl; arylalkylene in which the alkylene moiety has 1 to 3 carbon atoms and the aryl moiety is phenyl, 1-naphthyl or 1-indenyl; or R
is the expression or (In the formula, 1 of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ ,
2 or 3 are independently selected from lower alkyl, lower alkoxy, halo, nitro or haloalkyl having 1 to 3 carbon atoms and having 1 to 3 same or different halo atoms and the remainder are hydrogen and R ³ is a single bond or alkylene having 1 to 3 carbon atoms; R ¹ is hydrogen or substituted arylalkyl having 1 to 4 carbon atoms; alkyl; R ² is hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl; R ¹ and R ² together with adjacent nitrogen atoms form a saturated or unsaturated nitrogen heterocycle having 3 to 6 carbon atoms (one of which is a nitrogen atom and the rest are carbon atoms); X is hydrogen, halogen , or trifluoromethyl, and can take any position on the phenyl ring; and Y is lower alkyl, lower alkoxy, halo, 1
lower haloalkyl having ~4 carbon atoms and having 1 to 3 identical or different halogen atoms,
lower haloalkoxy having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms,
or lower haloalkylthio having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms, provided that when Y is halogen, R,
R ¹ and R ² are not all hydrogen, Y is other than trifluoromethyl, X is other than hydrogen, and R ¹ and R ² are each hydrogen, R is methyl,
ethyl, propyl, 2-halophenyl, 2-lower alkyl phenyl or 4-fluorophenyl) to the leaves of the plant or to the growing medium. A method of suppression or destruction. 25 General formula (wherein R is phenyl, 1-naphthyl, 1-indenyl, or or (In the formula, 1 of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ ,
2 or 3 are independently selected from lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 to 3 carbon atoms and having 1 to 3 same or different halo atoms and the remainder are hydrogen and R ³ is a single bond or alkylene having 1 to 3 carbon atoms); R ¹ is hydrogen or a substituted arylalkyl having 1 to 4 carbon atoms; R ² is hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl; R ¹ and R ² together with adjacent nitrogen atoms form a saturated or unsaturated nitrogen heterocycle having 3 to 6 carbon atoms, one of which is a nitrogen atom and the rest are carbon atoms; X is hydrogen, halogen or trifluoromethyl, and can take any position on the phenyl ring; and Y is lower alkyl, lower alkoxy, halo, 1
lower haloalkyl having ~4 carbon atoms and having 1 to 3 identical or different halogen atoms,
lower haloalkoxy having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms,
or lower haloalkylthio having 1 to 4 carbon atoms and having 1 to 3 identical or different halo atoms, provided that when Y is halogen, R,
R ¹ and R ² are not all hydrogen, Y is other than trifluoromethyl, X is other than hydrogen, and R ¹ and R ² are each hydrogen, R is methyl,
ethyl, propyl, 2-halophenyl, 2-lower alkyl phenyl or 4-fluorophenyl), comprising: under the reaction conditions. A method for producing the above-mentioned compound, which comprises bringing it into contact with a liquid carboxylic acid. 26. The method of claim 25, wherein the reaction is carried out in an inert organic solvent at a temperature of about 0 to about 100<0>C and the halo is bromine. 27. Process according to claim 26, characterized in that an excess of liquid carboxylic acid is used as inert organic solvent.