NL193833C - 5-Amino-3-oxo-4 (substituted phenyl) -2,3-dihydrofuran compounds with herbicidal activity and herbicidal composition containing these compounds. - Google Patents

Description

1 193833 5-Amino-3-oxo-4- (substituted phenyl) -2,3-dihydrofuran compounds with herbicidal action and herbicide preparation containing these compounds

The invention relates to 5-amino-3-oxo-4- (substituted phenyl) -2,3-dihydrofuran compounds with herbicidal action.

Such compounds are known from U.S. Pat. No. 3,239,538. The compounds described herein require dichloro substituents in position 2 of the furan ring. In addition, an unsubstituted phenyl substituent is present in position 4 of the furan ring.

Chemiker-Zeitung 104 (1980) No. 10, pp. 302-303 includes an article that the cyclization of 1- (dimethylamino) -2,4-diphenyl-1-butene-3,4-dione to form 5-dimethylamino-2,4-diphenyl- 2,3-dihydrofuran. Japanese patent application 69/13710 (Chemical Abstracts 71: 61195e (1976)) discloses the generic formula for 5-amino-3-oxo-4- (phenyl and halophenyl) -2,3-dihydrofuran and specifically describes 5-amino-3- oxo-4- (phenyl and chlorophenyl) -2,3-dihydrofurans with anti-convulsive effect. Helvetica Chemica Acta, Vol. 66, pp. 362-378 (1983) describes 5-N-cyclopropyl-4-phenyl-2-15 methoxycarbonylmethylene-3-furanone as part of an academic exposition of a chemical synthesis. U.S. Patent 4,441,910 describes herbicide uridosulfonyl furans and uridosulfonyl thiophenes.

The invention now provides compounds according to the preamble, characterized in that they have formula 1, wherein 20 R methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclohexyl, phenyl, naphth-1-yl, 2-fluorophenyl, 2- chlorophenyl, 2-methylphenyl, 2-trifluoromethylphenyl, 3-methylphenyl, 3-trifluoromethylphenyl, 4-fluorophenyl or 2,6 * difluorophenyl; R1 represents hydrogen, methyl, ethyl, propyl, propenyl or (1-ethoxycarbonyl) ethyl; R2 represents hydrogen, methyl or ethyl or R1 and R2 together with the nitrogen atom to which they are attached form an N-pyrrolidinyl group; X represents hydrogen or chlorine; and Y represents trifluoromethyl, chlorine, bromine, methyl, methoxy or isopropoxy; with the proviso that if Y is other than trifluoromethyl and X is other than hydrogen and R 1 and R 2 are each hydrogen, R methyl, ethyl, propyl, 2-chlorophenyl, 2-fluorophenyl, 2-methylphenyl or 4 -Fluorophenyl, and compatible salts thereof.

These compounds possess both pre-emergent and post-emergent herbicide activity and have particularly good pre-emergent herbicide activity against a broad spectrum of both broadleaf weeds and grassy weeds. In smaller dosages upon application, the compounds also exhibit plant growth regulating properties.

According to the present invention, it has been found that for herbicidal action it is necessary that the phenyl substituent be substituted in position 3. The comparative experiments described later show that if the 4-phenyl substituent is unsubstituted, as in the aforementioned U.S. Pat. No. 3,239,538, these compounds exhibit poor or no activity against virtually all weeds tested.

The invention also includes compatible salts of the compounds of formula 1, for example, salts obtained by replacing the amino hydrogen (i.e., R1 and R2 is hydrogen) with a compatible cation or by enolation of the 3-oxo group after substitutions of the amino hydrogen.

The compounds of formula 1 exist as keto <-> enolisomers. The compounds also have an asymmetric carbon atom and can also exist as optical isomers. In some cases, the compounds also exist as geometric isomers. Formula 1 aims to include the respective individual isomers as well as mixtures thereof, and the respective isomers as well as mixtures thereof are within the scope of the invention.

It is particularly preferred according to the invention when R represents phenyl, 2-fluorophenyl, 2-methylphenyl, 50 2-chlorophenyl or 2,6-difluorophenyl; R1 represents hydrogen, methyl or ethyl; R2 represents hydrogen; X represents hydrogen and Y represents trifluoromethyl. In particular, 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 the herbicide activity.

According to a further aspect of the invention, there is provided a herbicide composition consisting of a herbicidally effective amount of a compound of formula 1 or compatible salts thereof or of a mixture of such compounds and a compatible carrier.

To prevent or control the growth of unwanted vegetation, the growth medium and / or the foliage of such vegetation can be treated with a herbicidally effective amount of the compounds of formula 1 and / or compatible salts thereof.

Also, the compounds of the invention can be used to control plant growth, wherein the growth medium and / or foliage of such vegetation are treated with an effective amount to control the plant growth of the compounds of formula 1 and / or compatible salts thereof effective to modify the normal growth pattern of the plants.

The compounds of formula I, wherein R 1 and R 2 are each hydrogen and R represents the said aryl group, may be suitably prepared according to the process schematically shown in Figure 1, wherein X and V have the above meaning and Z 'have the said aryl group.

The rearrangement of a compound of formula 2 to a compound of formula 3 can be conveniently carried out by contacting the compound of formula 2 with a halogen, preferably bromine, and a liquid carboxylic acid in the presence of an inert organic solvent.

This process is usually carried out over a period of 4 to 36 hours, preferably 18 to 24 hours at temperatures ranging from 0 to 100 ° C, preferably 20 to 30 ° C, using 1.0 to 10.0 , preferably 1.0 to 1.1 moles, halogen per mole compound of the formula 2. Suitable liquid carboxylic acids which can be used are, for example, acetic acid, propionic acid, butyric acid and formic acid. When an excess of carboxylic acid is used, the excess can serve as a solvent or liquid carrier for this reaction system. Other organic solvents that can be used are, for example, liquid halogenated alkanes, for example dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane; liquid aromatics, for example benzene, toluene; liquid alkyl ethers, for example diethyl ether, dimethyl sulfoxide, dimethylformamide and compatible mixtures thereof.

Best results are obtained using bromine as the halogen, although chlorine and iodine could also be used

The starting materials of the formula II can be prepared according to the process shown schematically in Figure 2, wherein R 1 represents alkyl of 1 to 4 carbon atoms, aryl (e.g. phenyl) or arylalkylene (e.g. benzyl), and Z ', Y and X have the above meaning to own.

This process can be conveniently carried out by contacting a compound of the formula IV with a compound of the formula 5 and a strong base, preferably in an inert organic solvent.

This process is usually carried out in the course of 5 to 36 hours, preferably 18 to 24 hours, at temperatures ranging from 0 to 100oC, preferably 75 to 85 ° C, using 1.0 to 10.0, at preferably 1.0 to 1.2 moles of the compound of the formula 5 per mole of the compound of the formula 4. Usually 1.0 to 10.0 moles of base per mole of the compound of the formula 5 are used

Suitable strong bases which can be used are, for example, alkali metal alkoxide, for example sodium methanolate, sodium methanolate, potassium ethanolate, sodium hydride and potassium hydride. The strong base should preferably be a base which does not provide water as a by-product in this reaction system.

Suitable inert solvents which can be used are, for example, methanol, ethanol and propanol, tetrahydrofuran, dimethoxyethane, dioxane and compatible mixtures thereof. Suitably, the alkali metal alkoxide is prepared in situ by reacting an alkali metal with excess alkanol, which in turn serves as the solvent for the above conversion.

The starting materials of formulas 4 and 5 are generally known materials and can be prepared by known methods or obvious modifications thereof (namely, by replacing said starting materials with suitable starting materials). The preparation of the compound of formula 4 is described, for example, in Org. Syn. Coll., Part 1,107 (1941) and the preparation of the compound of formula 5 is described in Org., Syn. Coll., Vol. 1, 270 (1941).

The compounds of formula 1, wherein R 1 and R 2 are each hydrogen (compounds of formula 7), can be prepared according to the general method, which is schematically represented by the total reaction equation of Figure 3, wherein R and X and Y are the have the above meanings and R 5 represents lower alkyl, aryl (e.g. phenyl) or arylalkylene (e.g. benzyl).

This process can be conveniently carried out by contacting the compound of the formula IV with the compound of the formula 6 and a strong base (e.g. sodium methanol-55 late, sodium ethanolate), preferably in an inert organic solvent.

This process is usually carried out over a period of 5 to 36 hours, preferably 18 to 24 onions, at temperatures ranging from 0 to 100 ° C, preferably 75 to 85 ° C, using 1.0 to 10.0, preferably from 3 to 193833 from 1.0 to 1.2 moles of the compound of the formula 6 per mole of the compound of the formula 4. Suitable inert organic solvents which can be used are, for example, methanol, ethanol, propanol, tetrahydrofuran, dimethoxyethane and dioxane and compatible mixtures thereof.

Suitable bases which can be used for this process include the bases described above with respect to the reaction of the compound of formula 4 with the compound of formula 5.

The hydroxyesters of the formula 6 are generally known compounds and can be prepared by known methods or obvious modifications thereof (for example, using suitably substituted starting materials).

The compounds of formula 1, wherein R 1 and R 2 are hydrogen and R represents methyl, ethyl, n-propyt, isopropyl, n-butyl, cyclohexyl, may also be conveniently prepared according to the method shown schematically in Figure 4, wherein in formula 9 R '' represents methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclohexyl and R10 lower alkyl, preferably methyl.

This process can conveniently be carried out by contacting the compound of formula 8 with a cyclizing agent under reaction conditions, preferably in an inert organic solvent.

This process is usually carried out in the course of 10 to 120 minutes, preferably 10 to 30 minutes, at temperatures in the range of 0 to 200 ° C, preferably 115 to 120 ° C, using 1 to 10, preferably 1 to 2, moles of cyclizing agent per mole of the compound of formula 8. Suitable cyclizing agents which can be used are, for example, strong anhydrous acids, for example sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid and methanesulfonic acid. Best results are usually obtained using anhydrous sulfuric acid. Suitable inert organic solvents that can be used are, for example, acetic acid, propionic acid, butyric acid, toluene and xylene and compatible mixtures thereof.

The starting materials of formula (8) can be prepared according to the process shown schematically in Figure 5, wherein R '* and R10 have the above meaning, X' represents chlorine, bromine or iodine and M and M 'independently of each other are sodium or lithium .

Although this method is schematically represented as three steps, the steps are usually and conveniently performed in situ. As is also customary with such conversions, the conversions are preferably carried out under an inert gas (eg nitrogen) under substantially anhydrous conditions.

In the first step of this method, the compound of formula 10 is contacted with a non-nucleophilic base, preferably in an inert organic solvent. This step is usually carried out over 1/2 to 3 hours at temperatures in the range of 0 to 25 ° C using 1 to 2, preferably 1 to 1.3 mole equivalents of non-nucleophilic base per mole of the compound of the formula 10. Suitable non-nucleophilic bases which can be used are, for example, sodium hydride, potassium hydride, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide , lithium diethylamide, lithium diisopropylamide and sodium dimethylamide. Sodium hydride is generally preferred because it provides very good results and is readily available commercially. The alkali metal amides and also natural alkali metal hydrides are generally known compounds and can be prepared by obvious methods according to known methods. For example, the alkali metal amides can be prepared by reacting a secondary amine with an alkali metal alkyl.

Suitable inert organic solvents which can be used are, for example, tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether and diisopropyl ether and compatible mixtures thereof.

The second step can be carried out by contacting the compound of formula 11 with an alkyl base, preferably in an inert organic solvent. As noted above, this process step is performed, for example, in situ with the first stage reaction mixture. This second stage is usually carried out over 1 to 4 hours at temperatures in the range of -78 to 0 ° C using 1 to 2, preferably 1 to 1.3 mole equivalents of alkyl base per mole of the compound of the formula 11. Suitable alkyl bases which can be used are, for example, alkali metal alkyls and alkyl Grignard reagents. Preferably lithium n-butyl is used because it gives good results and is readily available on the market. Suitable solvents, which may be used, include those listed above with respect to the first stage.

The third step can be carried out by contacting the compound of the formula 12 with the appropriate R 1 -halide containing the desired R "group, preferably in an inert organic solvent. The third step is also usually performed in situ with the reaction mixture of the 193833 4 second stage.

The third stage of this process is usually carried out in the course of 1 to 18 hours, preferably 1 to 5 hours, at temperatures in the range of -30 to + 30 ° C, preferably 22 to 25 ° C, using 1 up to 10 moles, preferably 1 to 1.5 moles, R '"X' per mole of the compound of the formula 12. Suitable inert organic solvents include the above solvents which have been mentioned with respect to the first step of this process The halides, R "X, are generally known compounds and can be prepared by known methods or obvious modifications thereof (eg replacement by suitable reactants and solvents).

The starting materials of formula 10 can be prepared according to the process shown schematically in Figure 6, wherein R11 represents lower alkyl (preferably methyl) and R10, X and Y have the above meaning.

This process can be conveniently carried out by contacting the compound of the formula IV under reaction conditions with the compound of the formula 13 and a strong base, preferably in an inert organic solvent.

This process is usually carried out under the same conditions as described above with respect to the preparation of the compound of the formula 2 except that the reactant of the formula 13 is used instead of the reactant of the formula 5. The reactants of the formula 13 are simple alkyl alkoxyacetate esters, for example methyl methoxyacetate. The preparation of such compounds is well known.

The compounds of formula 1, wherein one or both R1 and R2 substituents are formula 14, may be prepared by alkylation of the amino group of the corresponding compounds of formula 7, as indicated in the reaction scheme of Figure 7, wherein R, R1 X and Y have the above meanings and R 2 'as defined for R 2, except hydrogen, R 2 Z "is an alkylating agent with the required radical R 2 * or a required radical R 1 if dialkylation is desired.

This process can be carried out by contacting the compound of the formula 7 with a suitable alkylating agent capable of alkylating primary or secondary amino groups.

This can be done, for example, by contacting the compound of formula 7 with R 2 iodide or bromide, preferably in an inert organic solvent and preferably in the presence of an acid-binding base. This process is usually conducted over 1.0 to 7.20, preferably 2.0 to 18.0 hours at temperatures within the range of 0 to 100 ° C, preferably 20 to 45 ° C. If monoalkylation is desired, usually 1.0 to 1.1 moles of the R 1 -halide reactant per mole of the compound of Formula 7 are used. If it is desired to alkylate both amino hydrogen atoms, usually 1.9 to 4.0 moles of R 1 -halide per mole of the compound of the formula 10 are used. Where it is desired to prepare a compound wherein R 2 * is alkoxyalkyl or alkylthioalkyi, it is preferable to use a large excess of R 1 -halide even if a monoalkylation is desired, for example 3 to 6 moles of R 2 Z 2 per moles of the compound of formula 7. Further alkylation can be carried out in a second stage if desired, and variations in R1 and R2 can also be brought about by first monoalkylating only and then alkylating with an alkylating agent with a different R1 group. compounds in which R 1 and R 2 together with the amino nitrogen atoms form a 40 N-pyrrolidinyl ring can be prepared using the required Z 2 CH 2 -Z ", wherein Z" is Cl or Br, as the alkylating agent. which can be used are, for example, dichloromethane, carbon tetrachloride or dichloroethane, while tetrahydrofuran is also useful Suitable acid binding bases which can be used, are, for example, the bases described above with respect to the conversion of the compound of formula 4 to compound 45 of formula 5 (Figure 2).

The compounds of formula 14, wherein R 1 represents, for example, methyl and R 2 represents hydrogen or methyl or ethyl, are advantageously prepared using a dialkyl sulfate as an alkylating agent.

This can be conveniently accomplished by contacting a compound of formula 1 wherein one or both of R1 and / or R2 are hydrogen with the desired lower alkyl sulfate in the presence of a strong base and preferably in an inert organic solvent in the presence of a phase transfer agent. This process is usually carried out at temperatures in the range of 0 to 100 ° C, preferably 20 to 45 ° C, using 1.0 to 4.0 moles of dialkyl sulfate per mole of the compound of the formula 1. Typically, a excess of 2.5 moles of base used. Preferably, this process is also carried out in an inert solvent, such as, for example, dichloromethane, carbon tetrachloride, 55 dichloroethane and tetrahydrofuran.

Suitable strong bases which can be used are, for example, sodium hydroxide, potassium hydroxide, sodium ethanolate, sodium carbonate and potassium carbonate. Suitable phase transfer agents are those which transfer hydrophilic ions to a lipophilic organic medium and include, for example, benzethyl triethylammonium chloride, tetra-n-butylammonium chloride and methyl trioctylamminium chloride.

The compatible salts of the formula I can otherwise be prepared by conventional methods, for example by treating the compound of the formula 1, wherein R 1 and / or R 2 are hydrogen, with a suitable strong base, such as, for example, n-butyl lithium, sodium hydride and potassium hydride having the desired cation by conventional methods of obtaining the corresponding R1 and / or R2 cationic salts. The enolate salts can be prepared by treating the R1 and / or R2 cationic salts with base according to conventional methods. Further variations in the salt cation can be brought about by ion exchange with an ion exchange resin with the desired cation.

In the above-described processes, it is generally preferable to separate the products in question before proceeding in the reaction process with the next step, except where the next step is described as an in situ step or expressly otherwise indicated. These products can be recovered from the respective reaction mixtures by any suitable separation and purification method, such as, for example, recrystallization and chromatography. Suitable separation and purification methods are illustrated, for example, in the examples described below.

Generally, the conversions described above are conducted as liquid phase conversions, and thus the pressure is generally irrelevant apart from affecting the temperature (boiling point) thereby, if the conversions are carried out under reflux. These conversions are therefore generally carried out under pressures of 300 to 3,000 mm Hg and suitably under atmospheric or ambient pressure.

It will also be understood that if typical or preferred operating conditions (eg reaction temperature, times, molar ratios and reactants, solvents, etc.) are reported, other operating conditions could also be used. Optimal reaction conditions (e.g., temperature, reaction time, molar ratios, solvents, etc.) may vary depending on the particular reactants or organic solvents used, but these can be determined according to routine optimization tests.

If optical isomer mixtures are obtained, the respective optical isomers can be obtained by conventional cleavage methods. Geometric isomers can be separated by the usual separation methods depending on the different physical properties between the geometric isomers.

As used in the description of the invention, the following terms have the following meanings unless expressly stated otherwise.

35 The term "room temperature" or "ambient temperature" denotes 20-25eC.

The compounds of the formula I exhibit both pre-emergent and post-emergent herbicide activity and show particularly good pre-emergent herbicide activity.

For post-emergent applications, the herbicide compounds are generally applied directly to the foliage or other plant parts. For pre-emergent applications, the herbicide compounds can be applied to the growth medium or expected growth medium for the plant. The optimal amount of the herbicide compound or composition will vary depending on the particular plant species and, if so, the degree of plant growth and the particular part of the plant to be contacted and the degree of contact. The optimal dosage can also vary with the general place or environment (e.g. sheltered places, such as greenhouses compared to open 45 places, such as fields) and the desired type and degree of control. In general, the compounds of the invention are applied in amounts from 0.02 to 60 kg / ha, preferably 0.02 to 10 kg / ha, for both pre- or post-emergent control.

While the compounds can be applied in the undiluted state in theory, they are also generally applied in practice as a composition or composition containing an effective amount of the compound (s) and an acceptable carrier. An acceptable or compatible carrier (acceptable for use in agriculture) is a carrier which does not significantly adversely affect the desired biological effect to be achieved with the active compounds other than dilution. Usually, the preparation contains 0.05 to 95% by weight of the compound of the formula 1 or mixtures thereof. Concentrates of high concentrations, which are intended to be diluted before use, can also be prepared. The carrier can be a solid, liquid or aerosol. The actual composition can be in the form of granules, powders, dusts, solutions, suspensions and aerosols.

193 833 6

Suitable solid carriers which can be used are, for example, natural clays (such as kaolin, attapulgite, montmorillonite), talken, pyrophyllite, diatomaceous earth, synthetic fine silica, calcium alumosilicate, tricalcium phosphate and the like. Organic materials such as walnut husk flour, cotton seed husks, wheat flour, wood measurement and wood bark flour can also be used as carriers.

Suitable liquid diluents that can be used are, for example, water, organic solvents (eg, hydrocarbons, such as benzene, toluene, dimethyl sulfoxide, kerosene, diesel oil, fuel oil, petroleum naphtha). Suitable aerosol carriers which can be used include conventional aerosol carriers, such as halogenated alkanes.

The compositions may also contain various promoters and surfactants which favor the rate of transport of the active compound into the plant tissue, such as, for example, organic solvents, wetting agents and oils, and in the case of preparations intended for run-out agents which reduce the leachability of the compound or otherwise promote stability in the soil.

The formulations may also contain various compatible adjuvants, stabilizers, conditioners, insecticides, fungicides and optionally other herbicidally active compounds.

In small doses, the compounds of the invention also exhibit plant growth regulating activity and can be used to modify the normal growth pattern of green plants.

The compounds of the formula I can be applied in pure form as plant growth regulators, but in a more pragmatic manner they are applied in combination with a carrier as in the case of use as a herbicide. The same types of carriers as described above with regard to the herbicide preparations can also be used. Depending on the desired application, the plant growth control composition may also contain other compatible ingredients or be applied with other compatible ingredients such as desiccants, defoliants, surfactants, adjuvants, fungicides and insecticides. The plant growth control composition will generally contain 0.005 to 90% by weight of the compounds of the formula 1, depending on whether the preparation is for direct application or for first dilution.

A better understanding of the invention can be obtained by the following non-limiting examples. Unless expressly stated enders, all temperatures and temperature ranges are expressed in degrees Celsius and the term "" ambient "or" room temperature "designates 20 to 25 ° C. The term" "percent" or "%" designates weight percent and the the term "mor * denotes gram molecules. The term" equivalent "denotes an amount of reagent, which is in moles equal to the number of moles of the reactant, preceded or subsequently elicited in the relevant example, expressed in finite number of moles or finite weight or volume. If stated, the magnetic proton nuclear magnetic resonance (NMR) spectrum is determined at 60 MHz, with the signals designated as singlets (s), broad singlets (bs), doublets (d), double doublets (dd), triplets (t), double triplets (dt), quartets (q) and multiplets (m) and Hz indicates the number of periods per second. Also, examples are repeated, if necessary, to provide further starting material for the following examples.

40

Examples

Example 1a (intermediate) (3-Trifluoromethylphenyl) -benzylcarbonyl-acetonitrile 45. In this example, 4.91 g of metallic sodium was added to 110 ml of anhydrous ethanol at room temperature and stirred until all sodium was dissolved. A mixture containing 18.76 g of (3-trifluoromethylphenyl) -acetonitrile and 21.73 g of ethyl phenylacetate was then added dropwise and the resulting mixture was stirred at reflux for 18 hours. The mixture was then poured into 300 ml of water and extracted three times with diethyl ether. The pH of the extracted aqueous layer was adjusted to pH 1 with 10% aqueous hydrochloric acid and extracted three more times with diethyl ether. The organic layer was washed twice with a saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated in vacuo to give 22.6 g of the title compound.

55 Example Ib 2-Phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5 * amino-2,3-dihydrofuran

In this example, a solution containing 21.8 g of (3-trifluoromethylphenyl) -benzylcarbonyl-acetonitrile dissolved 7 193833 in 60 ml of acetic acid was treated dropwise with a solution of 12.65 g of bromine in 20 ml of glacial acetic acid. The reaction mixture was stirred at room temperature for about 16 hours. The reaction mixture was poured into 250 ml of water and the resulting mixture was extracted three times with diethyl ether. The organic extracts were washed with a saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo to yield 8.4 g of a white solid which was dried to yield 7.0 g of the title compound (Table A : connection 1).

Example II

2 * Methyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran In a 500 ml three-neck round-bottom flask equipped with a mechanical stirrer, a dropping funnel and a reflux condenser, 100 ml of methanol were brought. 3.5 g of sodium were added to the stirred solvent. After all the metal was dissolved, a solution of 13.0 g of ethyl L - (+) - lactate and 18.5 g of (m-trifluoromethylphenyl) acetonitrile in 30 ml of ethanol was added dropwise to the reaction mixture. The mixture turned dark red and after the addition was finished, the mixture was refluxed for 18 hours. The mixture was then cooled to room temperature and added to 300 ml of water, after which the resulting mixture was acidified with 10% hydrochloric acid (pH 1). The mixture was then extracted with diethyl ether (ether) (three times) and the organic extracts were washed (twice) with a saturated aqueous sodium bicarbonate solution, 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 as a yellow powder. Two amounts of crystals were collected to give a total of 4.7 g of the title compound (Table A: Compound 25).

Example Illa1 (intermediate) 25 (3-Trifluoromethylphenyl) -methoxyacetyl-acetonitrile

In this example, 5.6 g of metallic sodium were added to 120 ml of anhydrous ethanol at room temperature under a nitrogen atmosphere, which led to hydrogen evolution. After the hydrogen evolution had ended, a mixture was added containing 30 g of (3-trifluoromethylphenyl) -acetonitrile and 18.5 g of methyl methoxyacetate in anhydrous ethanol, and the resulting mixture was refluxed for 3 to 4 hours. The mixture was then added to 300 ml of water and extracted three times with petroleum ether. The remaining water phase was acidified with aqueous 10% hydrochloric acid to a pH of 1 and extracted three times with diethyl ether. The diethyl ether extracts were combined, washed twice with a saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated. The concentrate was evaporated under very reduced pressure to give an oil which was triturated with diethyl ether. This mixture was then filtered to remove solids and the filtrate was evaporated in vacuo to provide 36.9g of the title compound as a brown solid.

Example Illa2 (intermediate) 40 (3-Trifluoromethylphenyl) -2-methoxyisovalerylacetonitrile

In this example, 10 g of (3-trifluoromethylphenyl) -methoxyacetyl-acetonitrile were added dropwise to a suspension of 1.87 g of sodium hydride in 20 ml of tetrahydrofuran at 0 ° C under a nitrogen atmosphere, leading to hydrogen evolution. After no more hydrogen evolution was observed, the mixture was cooled to -78 ° C and 24.3 ml of 1.6 M n-butyl lithium in hexane was added dropwise. The mixture was stirred at -78 ° C for 1½ hours and then at 0-4 ° C for an additional 20 minutes. Then, 3.9 ml (6.64 g) of 2-iodopropane were added dropwise and the mixture was stirred for 14-16 hours. The mixture was then added to water, acidified with aqueous 10% hydrochloric acid and extracted three times with diethyl ether. The extracts were combined, dried over magnesium sulfate and concentrated in vacuo to provide 11.4 g of the title compound as an oil.

50

Example IIIb 2-lsopropyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran

In this example, a mixture containing 11.4 (3-trifluoromethylphenyl) - (2-methoxyisovaleryl) acetonitrile and 7.8 g of concentrated sulfuric acid in 50 ml of acetic acid was refluxed for 30 minutes and then concentrated in vacuo . The concentrate was mixed with diethyl ether, washed three times with 1N sodium hydroxide in water, dried over magnesium sulfate and concentrated by evaporation to yield an oil. The oil was triturated in 20% (volume) ethyl acetate: 80% 193833 petroleum ether and left for 14-16 hours. The solid material was collected by filtration and washed three times with 20% (volume) ethyl acetate: 80% petroleum ether to yield 2.9 g of the title compound (Table A: Compound 42).

Example IV

2-Phenyl * 3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran

In this example, 1 g of solid sodium hydroxide in 4.0 ml of water was added to a mixture of 3 g of 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran in 50 ml of dichloromethane at room temperature, followed by addition of 1.19 g of dimethyl sulfate and 0.21 g of benzyl triethyl ammonium chloride. The resulting two phase mixture was stirred at room temperature for 2 hours and then washed three times with water, dried over magnesium sulfate and then concentrated in vacuo. The residue was then purified by silica gel chromatography, eluting mixtures of tetrahydrofuran and chloroform to give the title compound (Table A: Compound 2).

Example V

2- (2-fluorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-allylamino-2,3-dihydrofuran

To a mixture of 4.0 g of 2- (2-fluorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran in 80 ml of dichloromethane at room temperature, 1 g of sodium hydroxide in 4.0 ml of water was added, followed by addition of 1.44 g of allyl bromide and 0.27 g of benzyltriethylammonium chloride. The resulting two-phase mixture was stirred at room temperature for 18 hours, after which it was washed three times with water, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by chromatography on silica gel and eluting with chloroform to provide 2.5 g of the title compound (Table A: Compound 24).

Example VI

Lithium salt of 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran (R1 = CH3, R2 3 4 5 6 7 8 9 = Li)

In this example, 5.4 ml of 1.6 M n-butyl lithium in hexane were added dropwise with stirring to a solution at -30 ° C containing 2.86 g of 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran in 25 ml of tetrahydrofuran. The resulting mixture was stirred for 20 minutes and then concentrated in vacuo to provide 2.8 g of the title compound as a light brown solid. Elemental Analysis: Calculated: C = 63.74%, H = 3.84%, N = 4.13%; found: C = 61.82%, H = 4.90%, N = 3.48%.

35 VII

The compounds listed in Table A below were prepared using the required starting materials and the appropriate methods as described in the above examples.

TABLE A

40 Compounds of the formula 1 with Y = CF3- and X = H-

Basic analysis

Carbon Hydrogen Nitrogen Melting Point

45 No. R 'R2 R Ber. Gev. Ber. Gev. Ber. Gev. ° C

(Example) (I) UT H UT 63.95 64.66 3.76 4.19 4.39 4.78 182-184 * 2 (IV) CH, H 0 64.86 6422 4.20 4.65 4.20 3.79 154-155 3 50 3 CH, CH, 0 65.71 65.63 4.61 4.83 4.03 4.12 102-106 4 CH2CH, H 0 65.71 66.55 4.61 5.12 4.03 328 143-145 5 CHjCH, CHjCH, 0 67.20 67.76 5.33 5.63 3.73 3.77 115-120 6 Η H 4-F0 60.53 59.66 3.26 3.47 4.15 4.12 136-138 7 CH, H 2-F0 61.54 6 122 3.70 3.62 3.99 4.45 151-156 8 55 8 CH, CH, 2-F0 62.47 62.95 4.11 4.38 3.84 4.08 91- 93 9 CHjCH, H 2-F0 62.47 60.36 4.11 4.11 3.84 4.02 136-138 9 193833 TABLE A (continued). Compounds of the formula 1 with Y = CF3- and X = H-

Basic analysis 5 ------—--

Carbon Hydrogen Nitrogen Melting Point

No. R 'R * R Ber. Gev. Ber. Gev. Ber. Gev. ° C

(Example) 10 10 (CH2) 2CH3 H 2-FO 63.32 63.6 4.49 4.7 3.69 3.71 53-60 11 CHgCHa CHjCHj 2-F0 64.12 63.41 4.83 4.93 3.56 3.85 oil 12 CH3 H 2-CI0 58.78 58.52 3.54 3.63 3.81 4.05 201-204 * 13 CH3 H 2-CI0 * 59.77 59.67 3.93 4.05 3.67 3.72 116-119 14 CHjCH, H 2-00 59.77 60.5 3.93 4.05 3.67 3.89 131-137 15 15 CHjCHj CHjCHj 2-00 61.55 61.72 4.64 4.79 3.42 3.77 113-114 16 Η H 2-CH30 64.86 65.02 4.20 4.43 4.20 4.26 179-181 * 17 Η H 3-CH30 64.86 62.54 4.20 4.27 4.20 3.82 148-151 18 (not Η H 4-CH30 64.86 65.86 4.20 4.25 4.20 4.34 208-211 * according to 20 invention) 19 Η H 2-CF30 55.81 55.58 2.84 3.05 3.62 3.69 68-75 20 Η M 3-CF30 55.81 55.37 2.84 3.09 3.62 3.40 60-63 21 Η H 2.6- 57.46 57.45 2.82 3.14 3.94 4.16 225-227 * diF0 25 22 CHa H 2.6- 58.54 59.3 3.25 3.45 3.79 3.84 191-193 * diF0 23 CH2CH3 H 2.6- 59.53 60.11 3.66 4.00 3.66 3.71 63-65 diF0 24 (V) -CH2CH = CH2 H 2-F0 63.66 62.4 3.98 4.31 3.71 4.27 oil 30 25 (111) Η H CH3 56.03 56.54 3.89 4.22 5.45 5.52 129-130 26 (non-CH2C (CI) = CH2 H 0 61. 0 57.9 3.8 3.9 3.55 3.2 oil according to the invention) 27 (non-CH2CH = C (CI) CH3 H 0 61.8 61.3 4.2 4.7 3.4 3.1 134-138 35 according to the invention) 28 -CH (CH2) C00C2Hs H 0 63.0 61.5 4.8 5.0 3.3 3.2 Oil 29 (VI) UH -CH3 0 63.74 61.82 3.84 4.9 4.13 3.48 120 * 30 Η H 1-naphthyl 68.3 65.8 3.8 4.1 3.8 3.8 123-126 40 31 CH3 H 1-naphthyl 68.9 65.7 4.18 4.4 3.7 3.55 174 -179 32 CH3 CH3 1-naphthyl 69.5 69.2 4.5 4.7 3.5 3.6 139-143 33 (not Η Η H 54.32 54.91 3.29 3.54 5.76 5.42 145-146 * according to the invention) 45 34 (not CH3 Η H 56.03 55.75 3.89 4.04 5.45 5.39 158-159 according to the invention) 35 CHS H CH3 57.56 58.87 4.43 4.66 5.17 5.32 116-118 36 CH2CH3 H CH3 58.95 59.35 4.91 5.04 4.91 5.34 141-142 50 37 Η H CHjCHj 57.56 60.08 4.43 4.91 5.17 5.47 173-174 38 CHS H CH2CHa 58.95 59.59 4.91 5.12 4.91 5.17 138-139 39 Η H (CH2) 2CH3 58.95 60.26 4.91 5.19 4.91 5.08 165-168 40 CH3 H (CHJjCHa 60.20 612 5.35 5.84 4.68 4.56 oil 41 CH3 CH3 (CH2) 2CH.j) 61.34 61.82 5.75 6.11 4.47 4.46 oil 55 42 (III) Η H CHfCHaJj 58. 95 58.79 4.91 523 4.91 5.0 155-156 43 CH3 H CHtOyj 60.20 60.80 5.35 5.36 4.68 4.85 121-122 193 833 10 TABLE A (continued)

Compounds of formula 1 with Y = CF3 and XnH-Elemental analysis 5 --------

Carbon Hydrogen Nitrogen Melting Point

No. R1 R2 R Ber. Gev. Ber. Gev. Ber. Gev. ° C

(Example) 10 44 Η H (CHaJgCHs 60.20 61.42 5.35 5.68 4.68 4.9 137-138 * 45 CH3 H (CH2) 3CH3 61.34 62.84 5.75 6.17 4.47 5.03 90 46 CH3 H cyclohexyl 63.72 64.41 5.90 6.18 4.13 3.6 143-145 47 CHjCH3 H cyclohexyl 64.59 64.94 6.23 6.87 3.97 4.11 142-143 • decomposition -----—— 15 ** = 2-chlorophenyl

TABLEB

Compounds of formula 1 with X = H-2q Elemental analysis

Carbon Hydrogen Nitrogen Melting Point

No. R1 R2 R Y Ber. Gev. Ber. Gev. Ber. Gev. eC

48 Η H 2-CH20 Cl 68.11 68.64 4.67 4.97 4.96 175-177 25 49 Η H 2-F0 Cl 63.26 62.3 3.62 3.8 4.61 4.17 178-180 * 50 CH3 H 2-CI0 Cl 61.08 62.21 3.87 4.06 4.19 4.33 185-193 * 51 CH3 Η H Cl 59.07 59.1 4.48 4.95 6.27 6.24 117-120 * 52 CH2CH3 Η HO 60.64 61.11 5.05 5.52 5.90 6.03 177-178 53 Η H CH3 Cl 59.07 57.16 4.48 4.5 6.27 5.73 158-159 30 54 CHa H CHa Cl 66.64 62.11 5.05 5.42 5.90 6.05 119-122 55 Η H CH2CH3 Cl 60.64 58.69 5.09 5.46 5.89 5.67 152-155 56 CH3 H CHjCHa Cl 62.03 63.34 5.61 5.83 5.56 5.96 95- 97 57 CHj CHS CH2CH3 Cl 63.28 62.48 6.07 6.86 527 5.93 Oil 58 CH2CHa H CH2CH3 Cl 63.28 63.82 6.7 6.52 5.27 5.89 120-123 35 59 Η H (CH2) 2CH3 Cl 62.03 62.13 5.61 5.76 5.56 5.63 152-154 60 CHa H (CH2) 2CH3 Cl 63.28 63.58 6.07 6.49 5.27 5.86 Oil 61 CH2CHa H (CH2) 2CH3 Cl 64.40 65.34 6.49 7.11 5.01 5.33 104-106 62 CHa CHa (CH ^ CI ^ Cl 64.40 64.14 6.49 6.65 5.01 4.67 oil 63 Η H CHa (CHa) 2 Cl 62.04 63.69 5.57 6.05 5.57 6.37 156-157 4Q 64 CH3 H CH2 (CH3) 2 Cl 63.29 63.03 6.03 6.72 5.27 5.62 85-91 65 CH2CH3 H CH2 (CHa) a Cl 64.41 65.66 6.44 6.83 5.01 5.47 130-131 66 Η H 0 Br 58.20 54.8 3.84 3.79 4.24 3.97 177-178 * 67 CHa H 0 Br 59.32 60.79 4.07 4.36 4.07 3.93 181-185 68 CH2CH3 H 0 Br 60.35 61.01 4.47 4.74 3.91 3.53 161-163 45 69 Η H 2-00 Br 52.69 54.59 3.02 3.26 3.84 4.14 202-204 70 CHa H 2-00 Br 53.91 53.77 3.44 3.47 3.70 3.69 205-207 71 CH2CHa H 2-CI0 Br 55.05 55.3 3.82 3.97 3.57 3.51 144-147 72 Η H 2-F0 Br 55.19 55.14 3.16 3.57 4.02 3.94 190-191.5 73 CH3 H 2-F0 Br 56.37 58.0 3.59 3.41 3.87 4.51 172-173 5q 74 CH2CH3 H 2-F0 Br 57.46 57.59 3.99 4.31 3.72 3.57 157-159 75 Η H 2-CH30 Br 59.32 58.48 4.07 422 4.07 4.03 165-167 76 CH3 H 2-0 * 30 Br 60.35 60.36 4.47 4.68 3.91 3.96 208-210 77 CH2CHa H 2-0 * 30 Br 61.31 62.98 4.84 5.16 3.76 424 140-142 78 CHa HH Br 4921 4801 373 441 523 5 06 109-118 55 79 CH2CH3 Η H Br 51.08 50.35 426 428 4.97 4.86 172-175 * 80 Η H 0 CHS 77.0 76.3 5.7 5.9 5.3 5.1 137-141 11 193 833 TABLE B (continued)

Compounds of Formula 1 with X = H-Elemental Analysis 5 Carbon Hydrogen Nitrogen Melting Point

No. R1 R2 R Y Ber. Gev. Ber. Gev. Ber. Gev. ° C

81 CH3 H 0 CHS 77.4 77.1 6.1 6.4 5.0 5.1 150-152 82 Η H 0 OCHs 72.6 73.7 5.4 6.6 5.0 5.1 141-144 10 83 CHg H 0 OCHa 732 72.5 5.8 5.9 4.7 3.6 128-133 84 CH3 H 0 - OCHJCHJj 74.30 70.02 6.5 6.47 4.33 4.21 185-188 * 85 CH2CH3 H 0 OCHICHJJ 7425 75.88 6.87 7 2 3 4.15 4.23 111-113 86 Η H 2-CHs0 OCHfCHg) 7428 73.58 6.55 6.85 4.33 4.17 149-151 87 CHg H 2-CH30 0CH ( CH) 2 74.75 74.35 6.82 6.95 4.15 3.83 134-135 15 88 Cf ^ CHa H 2-CHj, 0 OCHfCH ^ 75.19 73.63 7.17 727 3.99 4.19 134-136 89 Η H 2-F0 OCHfCHJ, 69.71 70.7 5.54 5.74 4.28 4.25 150- 151 90 CH3 H 2-F0 OCH (CHj) 70.37 69.66 5.91 6.1 4.10 4.25 191-193 91 Η H 2-CI0 OCHfCHgJj 66.38 68.29 4.07 4.36 5.28 5.48 171-173 92 Η H CH3 OCHfCHsk 68.0 65.75 6.9 6.6 5.7 5.6 151-155 20 93 CH3 H CHa OCHfCHJj 68.97 68.69 7.28 8.01 5.36 6.15 114-115 94 (not Η H 0 -00 76.95 76.3 5.0 6.0 4.1 3.0 73-78 according to the invention) 95 (not CHS H 0 -O0 77.3 73.9 5.3 5.6 3.9 4.1 163-167 according to the invention) 961 CHS CH3 0 Y = CI, 62.1 62.9 4.3 4.7 4.0 4.0 133-137

X = CI

97 -CHi-iCFUCHa- O -CF3 67.55 72.4 4.85 5.1 3.75 3.8 105-111 35 96 'is 2-phenyl-3-oxo-4- (3,4-dichlorophenyl) -5-dimethylamino-2,3-dihydrofuran * = decomposition

TABLE C

Compounds of formula 1 with X = H

40 —--

Basic analysis

Carbon Hydrogen Nitrogen Melting Point

No. R1 R2 R Y Ber. Gev. Ber. Gev. Ber. Gev. ° C

45 C-1 CH3 CH3 0 H 77.42 75.64 6.09 6.39 5.02 5.03 111-115 C-2 Η Η Η H 68.57 68.99 5.14 5.78 8.0 7.87 221-223 * C-3 Η Η H 3-CI 57.29 51.6 6.68 5.67 3.82 3.7 214 -216 * C-4 ** Η Η H 4-CI 57.29 53.46 6.68 5.52 3.82 4.11 169-170 * C-5 CH3 Η H 4-CI 59.07 59.34 4.48 5.03 6.27 6.02 133-137 * 50 C-6 CH3 CH3 H 4-CI 60.64 58.61 5.05 5.24 5.90 5.76 161-163 C-7 CH3 H 0 4-CI 68.1 64.4 4.7 5.3 4.7 4.5 oil C-8 Η Η H 4-CH3 69.84 67.98 5.82 5.63 7.41 6.7 189-191 * C-9 CH3 Η H 4-CH3 70.94 70.85 6.4 6.63 6.9 6.96 151-156 * C-10 Η H 0 4-CH3 77.0 76.2 5.7 5.9 5.3 5.05 142-146 55 —— i 193833 12 TABLE C (continued)

Compounds of formula 1 with X = H Elemental analysis 5 C-11 CH3 H 0 4-CH3 77.4 75.49 6.1 6.14 5.0 4.89 148-154 012 Η H 0 4-OCH372.6 70.5 5.4 6.0 5.0 4.8 138-141 013 CH3 CH3 0 4-OCH373.8 72.9 6.2 6.7 4.5 4.7 140-143 014 *** H 0 3-CFg 62.7 62.4 3.4 4.5 6.35 5.8 Oil 015 CH3 CH3 R = 0.3 CF3 59.76 57.9 3.93 4.06 3.67 3.56 oil

10 FT = CL

ΟΙ 62 Η H 0 Y = 3-CI, 60.0 60.1 3.5 3.7 4.4 4.8 179-182

X = 4-CI

C-162 is 2-phenyl-3-oxo-4- (314-dichkx) rphenyl-5-amino-2l3-dihydroturan 15 * * »decomposition ** (described in JP-A 69-13710) ** = = 4 -NOa0-

In this test, the compounds of Table A were tested for pre-emergent and post-emergent activity against a number of grasses and broadleaf plants including one grain and one broadleaf crop, using the procedures described below. The compounds tested are indicated by the compound number in Table A above.

tl

Pre-emergent herbicide test The pre-emergent herbicide activity was determined in the following manner.

Test solutions of the respective compounds were prepared as follows: 355.5 mg of the test compound was dissolved in 15 ml of acetone. 2 ml of acetone, containing 110 mg of nonionic surfactant, were added to this solution. Then, 12 ml 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 vegetation were planted in a pot of soil and the test solution was sprayed evenly on the soil surface either at a dose of 27.5 µg / cm 2 or in some cases, as indicated in Table D below, with some of the compounds in a smaller doses of 15.6 pg / cm2 were investigated. The pot was poured and placed in a greenhouse. The pot was watered at 35 intervals and observed on the sprouting of seedlings, the health of the sprouting seedlings, for a period of 3 weeks. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A scale of O to 100 was used, with O indicating no phytotoxicity and 100 indicating complete death. The results of these tests are summarized in Table D.

40

Post-emergent herbicide trial

The compound to be tested was formulated in the same manner as described above for the pre-emergent trial. This preparation was sprayed evenly on two equal pots, containing plants with a height of 5 to 7½ cm (except wild oats, soybeans and Paspalem grass, which were 45 7½ to 10 cm high) (15 to 20 plants per pot), in a dose of 27.5 pg / cm2. After the plants became dry, they were placed in a greenhouse and then, if necessary, watered at intervals. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to treatment. After 3 weeks, the herbicidal effectiveness of the compound was rated based on these observations. A scale of 0 to 100 was used, 50 indicating 0 no phytotoxicity and 100 indicating total death. The results of these tests are summarized in Table E.

13 193833

TABLE D

Pre-emergent herbicide activity

Applied dose: 27.5 pg / cm2, unless stated differently 5 ----

Broad-leaved plants Grasses

Phytotoxicity,% Phytotoxicity,% 10 Compound no. Moss-out papaya soy-hairy Wild rice Standing tender seed jay beans finger palm oat reported herb grass grass 1 94 100 100 95 100 100 100 93 15 2 100 100 100 100 100 100 100 100 3a 98 100 100 60 100 80 100 60 4a 95 100 100 98 100 100 100 75 5 100 80 100 20 100 70 100 20 6 100 100 100 85 100 100 100 85 20 7® 100 100 100 100 100 100 100 100 8a 98 100 100 100 100 100 100 70 ga 100 100 100 100 100 100 100 100 10 100 100 100 90 100 100 100 90 11a 90 50 100 60 100 50 60 20 25 12® 100 100 100 90 100 100 100 95 13a 100 100 100 100 100 100 100 95 14a 100 100 100 70 100 100 100 95 15a 95 90 100 20 100 50 70 0 16 100 100 100 85 100 100 100 95 30 17 99 83 98 55 100 70 63 55 18 (not according to the 0000000 0 invention) 19 “100 80 100 20 98 100 100 90 20 100 100 100 75 98 65 85 50 35 21 95 90 25 40 100 100 100 80 22 100 100 100 100 100 100 100 100 23 100 100 70 100 100 100 95 24a 98 90 100 65 100 95 70 55 25 90 98 85 90 100 88 80 65 40 26 (not according to the 95 75 100 30 0 95 0 30 invention) 27 (not according to the 0000000 0 invention) 28 99 98 100 45 99 48 67 45 45 29 98 97 100 98 100 100 90 100 30 98 55 100 25 78 55 55 15 31 100 100 100 80 100 100 95 80 32 95 80 100 25 100 80 60 75 33 (not according to the 95 100 70 78 98 80 90 78 50 invention) 34 (not according to the 100 100 100 100 100 100 100 100 invention) 35 100 100 100 100 100 100 100 100 36 100 100 100 100 100 100 100 100 55 37 100 100 100 85 98 98 98 70 38 100 100 100 100 100 100 100 100 193 833 14 TABLE D (continued)

Pre-emergent herbicide activity

Applied dose: 27.5 pg / cm2, unless stated differently 5 - - - -

Broad-leaved plants Grasses

Phytotoxicity,% Phytotoxicity,% 10 Compound no. Moss-out tape- soy hairy Pas- Wild Rice standing tender seed jay beans finger palm oats reported herb grass grass 39 100 100 100 70 100 100 100 88 15 40 100 100 100 100 100 100 100 100 41 100 100 100 50 100 100 100 65 42 95 100 100 25 35 88 10 0 43 100 100 100 100 100 100 100 100 44 90 100 100 15 98 99 75 10 20 45 100 100 100 93 100 100 100 100 46 100 100 100 70 100 100 90 70 47 100 55 60 30 100 95 70 48 60 65 30 75 25 25 25 93 j 49 100 100 100 100 100 100 100 100 I 25 50 100 100 100 100 100 100 100 100 j 51 100 100 100 98 100 100 100 95 52 100 100 100 100 100 100 100 100 53 60 65 50 35 0 15 0 0 54 100 100 100 93 100 100 100 97 30 55 55 50 0 25 73 20 0 0 56 100 100 100 100 100 100 100 80 57 98 100 100 45 100 65 30 40 58 100 100 75 90 100 100 85 90 59 50 45 0 0 60 15 0 0 35 60 100 100 100 99 100 100 100 97 61 100 100 85 93 100 100 80 93 62 100 100 100 45 100 94 50 30 63 25 45 0 0 20 20 0 0 64 98 100 100 93 100 100 95 60 40 65 100 100 100 90 100 100 100 85 66 100 100 100 70 100 95 98 90 67 100 100 100 100 100 100 100 100 68 100 100 100 100 100 100 100 69 69 100 98 99 75 100 100 99 85 45 70 100 95 90 90 100 100 100 95 71 100 95 97 70 100 100 95 93 72 100 100 99 85 100 100 100 99 73 100 100 100 100 100 100 93 100 74 100 100 80 93 100 100 98 97 50 75 100 99 100 50 100 100 98 95 76 100 93 85 90 100 100 99 93 77 100 99 98 85 100 100 94 93 78 100 98 70 90 100 100 100 98 79 100 100 100 100 100 100 100 100 55 80 25 20 0 0 95 25 10 0 81 100 100 100 100 100 100 100 0 15 193 833 TABLE D (continued)

Pre-emergent herbicide activites

Applied dose: 27.5 pg / cm2, unless stated differently 5 ----

Broad-leaved plants Grasses

Phytotoxicity,% Phytotoxicity,% 10 Compound no. Moss-out tape- soy hairy Pas- Wild Rice standing tender seed jay beans finger palm oats reported herb grass grass 82 80 55 20 45 98 25 20 0 15 83 100 100 100 70 100 100 100 0 84 99 95 100 98 100 100 100 97 85 100 97 100 97 100 100 99 97 86 100 100 100 85 100 100 90 75 87 100 95 100 95 99 100 98 80 20 88 100 100 90 100 100 98 90 89 100 100 100 99 100 100 100 100 90 100 100 100 100 100 100 99 99 91 99 100 100 97 100 100 95 97 92 20 20 0 25 0 0 0 0 25 93 100 100 100 100 100 100 100 93 94 ( not according to the 75 55 98 0 90 30 0 0 invention) 95 (not according to the 100 100 100 55 100 100 75 40 invention) 30 96 93 50 100 0 100 60 30 0 97 100 100 100 70 100 100 99 80 a = tested at 15.6 Mg / cm2 TABLE D '35 Comparative Compound Pre-emergent Herbicide Activity

Applied dose: 27.5 pg / cm2, unless stated otherwise Broad-leaved plants Grasses 40 _

Phytotoxicity,% Phytotoxicity,%

Compound no. Mustard- pape- soy- hairy Pas- Wild Rice standing seed jay- beans finger- palm oats 45 reported herb grass grass C-1 40 25 40 0 75 0 0 0 C-2 00000000 C-3 00000000 50 C-4 00000000 C-5 00000000 C-6 00000000 C-7 00000000 C-8 30 250400000 55 C-9 00000000 193833 16 TABLE IΎ (continued)

Comparative Compound Pre-Emergent Herbicide Activity

Applied dose: 27.5 pg / cm2, unless stated otherwise 5 -—---- C-10 0 0 0 0 oooo C-11 0000 30 000 G-12 00000000 C-13 00000000 10 C-14 0 0 0 0 45 35 0 0 C-15 00000000 016 00000000

TABLE E

^ Post-emergent herbicide activity

Applied dose: 27.5 pg / cm2, unless stated otherwise Broad-leaved plants Grasses 20 ____

Phytotoxicity,% Phytotoxicity,%

Compound no. Moss-pape- soy- hairy Pas- Wild Rice standing tender- jay- beans finger- palm- oats 23 reported seed herb grass grass 1 60 100 50 50 40 33 45 20 2 85 100 92 90 58 60 60 42 3 “70 90 75 65 0 0 0 0 30 4a 60 95 75 80 50 65 65 45 5 80 90 70 60 30 30 30 0 6 60 80 60 40 45 60 60 20 7 ° 95 100 98 100 80 80 90 80 8a 65 100 65 80 40 65 65 20 35 9a 80 95 90 90 70 90 90 60 10 90 100 90 80 30 0 30 0 11a 90 90 90 80 30 20 20 20 12a 100 100 90 90 90 40 50 20 13 “90 100 90 90 30 50 0 0 40 14 “80 90 90 70 50 80 90 40 15“ 80 90 80 70 20 0 0 0 16 65 95 60 55 70 80 75 20 17 35 73 35 30 0 0 0 0 18 (not according to 00 000 00 0 43 invention) 19 “55 45 45 0 55 45 40 0 20 43 80 45 33 0 0 0 0 21 50 30 60 50 30 0 0 0 22 80 80 70 70 60 90 70 0 50 23 85 100 90 80 70 100 60 30 24 “85 80 75 65 40 35 0 0 25 25 50 NT * 50 0 0 0 0 26 (not according to the 40 55 60 45 0 0 0 0 invention) 55 _____ - —-- 17 193833 TABLE E (continued ). Post-emergent herbicide activity

Applied dose: 27.5 pg / cm2, unless stated differently 5 _—---------

Broad-leaved plants Grasses

Phytotoxicity,% Phytotoxicity,% 10 Compound no hoss-tape- soy-hairy Pas- Wild Rice standing tender- bean beans finger- palm oat seed reported Herb grass grass 27 (not according to 50 30 35 0 0 0 0 0 15 invention) 28 35 40 0 0 0 0 0 0 29 75 100 100 80 70 85 65 52 30 30 45 45 45 10 30 20 0 31 70 80 80 70 30 40 20 0 20 32 40 40 35 35 0 0 0 0 33 (not according to the 70 65 42 50 35 40 60 45 invention) 34 (not according to the 85 100 85 85 80 92 89 60

invention) I

25 35 100 100 100 100 100 90 98 75 36 75 98 70 70 65 80 65 35 37 50 50 45 40 0 0 0 0 38 85 100 100 70 75 75 75 65 39 47 60 40 0 0 0 0 0 30 40 95 100 98 80 95 95 95 95 41 90 100 90 90 45 75 75 30 42 11 0 10 25 0 0 0 0 43 80 100 75 95 90 80 90 45 44 25 25 25 20 0 0 0 0 35 45 75 95 90 90 55 75 65 0 46 50 50 50 40 20 25 0 0 47 70 70 70 85 40 30 35 15 46 60 65 30 30 25 25 25 0 49 75 90 80 40 60 60 30 75 40 50 85 90 90 65 80 85 80 55 51 50 50 40 60 30 25 25 0 52 95 100 95 85 60 60 75 25 53 30 15 0 33 0 0 0 0 54 60 87 75 73 35 40 0 0 45 55 00000000 56 55 93 70 90 0 0 0 0 57 30 45 85 70 0 0 0 0 58 45 50 30 65 0 0 0 0 5g 00000000 50 60 75 98 80 80 20 20 0 0 61 75 85 80 90 30 25 10 10 62 45 60 60 70 0 0 30 0 63 0 0 0 0 0 0 0 0 64 70 80 65 75 0 0 0 0 55 65 55 60 40 55 0 0 0 0 66 50 65 50 45 0 0 0 0 193 833 18 TABLE E (continued)

Post-emergent herbicide activity

Applied dose: 27.5 pg / cm2, unless stated otherwise 5 -—---— —-

Broad-leaved plants Grasses

Phytotoxicity,% Phytotoxicity,% 10 Compound no hoss-tape- soy-hairy Pas- Wild Rice standing tender- bean beans finger- palm oats reported seed herb grass grass 67 95 100 95 95 93 90 90 70 15 68 93 98 85 75 75 70 75 20 69 75 93 75 70 0 0 0 0 70 95 95 90 85 25 20 20 10 71 80 93 55 80 25 20 10 10 72 45 93 50 30 30 35 35 20 20 73 93 100 70 93 30 55 45 25 74 NT1 NT1 ------ 75 65 75 70 55 25 30 30 20 76 90 85 80 25 20 20 0 77 85 100 90 75 25 20 20 20 25 78 90 98 85 75 20 20 20 0 79 90 60 80 93 60 70 70 25 80 0 20 0 20 0 0 0 0 81 70 98 85 80 35 65 65 25 82 20 25 35 30 0 0 0 0 30 83 75 100 75 85 35 20 55 0 84 60 30 45 40 63 55 40 30 85 75 40 45 90 45 45 35 0 86 40 65 35 30 0 0 0 0 87 90 90 90 90 65 70 70 25 35 88 80 65 55 85 20 20 10 10 89 85 98 90 88 0 65 90 0 90 85 70 50 83 55 65 70 30 91 83 98 85 75 25 60 78 10 92 0 0 0 0 0 0 0 0 40 93 70 80 65 80 30 35 25 0 94 (not according to 25 20 20 20 0 0 0 0 invention) 95 (not according to the 65 65 65 40 25 20 0 0 invention) 45 96 65 7 0 70 55 0 0 0 0 97 70 80 65 55 0 0 0 0 = tested at 15.6 Mg / cm2 N.T.1 b not tested 50

Claims (3)

19 193833 TABLE E '• Comparative Compounds Post-Emergent Herbicide Activity Applied Dose: 27.5 pg / cm2 Unless Otherwise Specified 5 Broad-leaved plants Grasses Phytotoxicity,% Phytotoxicity,% Compound no. Moss-out soy-hairy Pas wild rice 10 standing terd seed jay herb beans finger grass palem grass oats reported C-1 20 20 0 25 0 0 0 0 C-2 00000000 / 5 03 00000000 C-4 00000000 C-5 00000000 C-6 00000000 C-7 00000000 20 08 25 20 25 30 0 0 0 O C-9 20 20 10 25 0 O 0 0 C-10 00000000 C-11 20 0 0 20 0 0 0 O C-12 00000000 C-13 00000000 C-14 00000000 C-15 25 25 0 30 25 10 45 45 C-16 00000000 30 As shown in Table D above, the compounds of the invention exhibit a broad spectrum of action of excellent pre-emergent phytotoxic activity, which is particularly true for compounds Nos. 2, 4, 7, 9, 12, 14, 16, 22. In addition, as shown in Table E, the compounds also generally exhibit post-emergent phytotoxic activity against broadleaf plants and in some cases also against grasses, which is especially true for compounds Nos. 7, 9, 12, 14, 16, 22 and 23. It also appears that the corresponding comparative compounds have a much poorer activity than the corresponding compounds according to the present invention. 40 Claims 1. 5-Amino-3-oxo-4- (substituted phenyl) -2,3-dihydrofuran compounds with herbicidal action, characterized in that they have formula I, wherein R is methyl, ethyl, n-propyl, isopropyl, n -butyl, cyclohexyl, phenyl, naphth-1-yl, 2-fluorophenyph, 2-chlorophenyl, 2-methylphenyl, 2-trifluoromethylphenyl, 3-methylphenyl, 3-trifluoromethylphenyl, 4-fluorophenyl or 2,6-difluorophenyl; R1 represents hydrogen, methyl, ethyl, propyl, propenyl or (1-ethoxycarbonyl) ethyl; R2 represents hydrogen, methyl or ethyl or R1 and R2 together with the nitrogen atom to which they are attached form an N-pyrrolidinyl group; 50. represents hydrogen or chlorine; and Y represents trifluoromethyl, chlorine, bromine, methyl, methoxy or isopropoxy; with the proviso that if Y is other than trifluoromethyl and X is other than hydrogen and R 1 and R 2 are each hydrogen, R methyl, ethyl, propyl, 2-chlorophenyl, 2-fluorophenyl, 2-methylphenyl or 4- fluorophenyl, 55 as well as compatible salts thereof. 193 833 20 A compound according to claim 1, wherein R represents phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-methylphenyl or 2,6-difluorophenyl; R1 represents hydrogen, methyl or ethyl; R2 represents hydrogen; 5. represents hydrogen and Y represents trifluoromethyl; as well as compatible salts thereof. Herbicide preparation consisting of a herbicidally effective amount of a compound according to claim 1 or 2 of a mixture thereof and a compatible carrier. Hereby 2 sheets drawing