NL8401876A - 5-AMINO-3-OXO-4- (SUBSTITUTED PHENYL) -2,3-DIHYDROFURAN COMPOUNDS, METHOD FOR THE PREPARATION THEREOF AND USE THEREOF AS HERBICIDE. - Google Patents

Description

τ Tl N.O. 32574 - 5-Amino-3-oxo-4- (substituted phenyl) -2,3-dihydrofuran compounds, process for their preparation and use as a herbicide.

The invention relates to 5-amino-3-oxo-4- (substituted phenyl) -2,3-dihydrofuran derivatives and to the use of such compounds as herbicides and as plant growth regulators.

5 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. British Patent No. 1,521,092 describes certain 5-substituted 3-phenyl-4 (1H) -pyridones or thions as 10 herbicides. Japanese patent application 13,710/69 (Chemical Abstracts 71i61195e) 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 4-chlorophenyl) -2,3-dihydrofurans. Japanese Patent No. 19,090 (Chemical Abstracts 69P10352e) discloses certain 2,3-dihydrothiophenes as pharmaceuticals. Helvetica Chemica Acta, Vol. 66, pp. 362-378 (1983) describes 5-N-cyclopropyl-4-phenyl-2-methoxycarbonyl-methylene-3-furanone as part of an academic exposition of a chemical synthesis. U.S. Patent No. 4,441,910 describes herbicide uridosulfonyl furans and uridosulfonyl thiophenes.

The invention provides compounds with both pre-emergent and post-emergent herbicidal activity and with particularly good pre-emergent 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.

The compounds of the invention may be represented by the formula 1, wherein R is lower alkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, lower alkenyl, haloalkyl of 1 to 4 carbon atoms and 1 to 3 halogen, which is independent of 30 are selected from the group consisting of: fluorine, chlorine, bromine and iodine, haloalkyl with 2 to 4 carbon atoms and 1 to 3 halogen atoms, which are independently selected from the group: fluorine, chlorine, bromine and iodine, lower alkoxy, lower alkylthio, lower alkoxyalkyl, in which the alkoxy and alkyl radicals thereof independently have 1 to 3 carbon-35 atoms, lower alkylthioalkyl, in which the alkyl radicals independently have 1 to 3 carbon atoms, phenyl, naphth-1-yl, ind -1-yl, 4-fluorophenyl, arylalkylene of 1 to 3 carbon atoms in the 8401876 2 alkylene radical and wherein the aryl radical is phenyl, naphth-1-yl or inden-1-yl, or substituted aryl or arylalkylene selected from the group containing the formulas 2, 3 and 4, wherein in these formulas one, two or three of R *, R8, R8, R ^, R8 and R9 are independently selected from the group: lower alkyl, lower alkoxy, halogen, nitro and haloalkyl of 1 to 3 carbon atoms and 1 to 3 equal or different halogen atoms, and the remaining hydrogen, and R 8 is a single bond or an alkylene of 1 to 3 carbon atoms; R * represents hydrogen or alkyl of 1 to 4 carbon atoms; R8 hydrogen, 10 alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkoxycarbonylalkyl of 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the alkyl radical, alkoxyalkyl, wherein the alkoxy and alkyl radicals are independently 1 to 3 have carbon atoms, or alkylthioalkyl, wherein the alkyl radicals independently have from 1 to 15 carbon atoms; or R 8 and R 8 together with the nitrogen atom to which they are attached form a saturated or unsaturated heterocyclic nitrogen containing 3 to 5 ring, one atom of which is nitrogen and the other carbon atoms; X represents hydrogen, lower alkyl, lower alkoxy, halogen or trifluoromethyl and may be present at any available location on the phenyl ring; and Y lower alkyl, lower alkoxy, halogen, lower haloalkyl of 1 to 4 carbon atoms and 1 to 3 equal or different halogen atoms, lower haloalkoxy of 1 to 4 carbon atoms and 1 to 3 equal or different halogen atoms or lower haloalkylthio with 1 to 4 carbon atoms 25 represents atoms and 1 to 3 equal or different halogen atoms; with the proviso that if Y represents halogen, R, R - * - and R8 are not all hydrogen and further, with the proviso that if Y is other than trifluoromethyl and X is other than hydrogen and R1 is hydrogen and R8 is hydrogen, R represents methyl, ethyl, propyl, 2-halophenyl, 2-lower alkylphenyl or 4-fluorophenyl.

The invention also includes compatible salts of the compounds of formula 1, for example salts, which are obtained by replacing the amino hydrogen (namely R 1 and R 8 is hydrogen) with a compatible cation or by enolation of the 3-oxo group after replacement. went from the amino hydrogen.

The compounds of the formula I exist as keto-enol isomers. 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 at the respective individual isomers as well as 84 0 1 8 7 6 f ·? To comprise 3 mixtures thereof and the respective isomers as well as mixtures thereof fall within the leader of the invention.

It has also 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.

According to a further aspect of the invention, there is provided a herbicidal composition which consists of a compatible carrier and an herbicidally effective amount of the compounds of formula II or compatible salts thereof or mixtures thereof.

The invention also provides a method of preventing or controlling the growth of unwanted vegetation, characterized in that the growing medium and / or foliage of such vegetation is treated with an herbicidally effective amount of the compound (and ) of the formula 1 and / or compatible salts thereof.

According to another aspect of the invention, there is provided a plant growth control composition characterized by a compatible carrier and a plant growth controlling amount of the compound of the formula 1, compatible salts of the formula 1 or mixtures thereof, which is effective to change the normal growth pattern of the plants.

The invention also provides a method of controlling the plant growth, which is characterized in that the growing medium and / or the foliage of such a vegetation is treated with an effective amount for controlling the plant growth of the compound (and ) of the formula 1 and / or compatible salts thereof, which is effective in modifying the normal growth pattern of the plants.

The invention also provides chemical intermediates and methods of preparing the compounds of the formula 1.

The invention will be described in more detail below.

Examples of typical compounds of the formula according to the invention can be found in Examples II, III and VI-X below.

Expressed in the substituents, the compounds are preferred, wherein R is lower alkyl, aryl or substituted aryl, preferably methyl, ethyl, propyl, phenyl or substituted phenyl and especially phenyl, monomethyl phenyl or monohalo phenyl, especially methyl, ethyl, n propyl, 2-halophenyl, 2-lower alkylphenyl or 4-fluorophenyl; R * and 40 R 4 independently of each other are hydrogen, methyl, ethyl or n-propyl for 8401876 <. "4 sets and preferably one of R * or is hydrogen and the other hydrogen is methyl, ethyl or n-propyl, preferably hydrogen, methyl or ethyl, especially methyl; X is hydrogen and / or Y represents 3-trifluoromethyl or 3-halogen, in particular 3-trifluoromethyl. Most preferred substituents contain a combination of two or more preferred substituents.

The compounds of formula I, wherein R * and R 1 are each hydrogen and R represents aryl or substituted aryl, may be conveniently prepared according to the method schematically shown in Figure 1, wherein X and Y have the above meanings and Z 'represents aryl or substituted aryl.

The rearrangement of a compound of formula 5 to a compound of formula 6 can be conveniently carried out by contacting the compound of formula 5 with a halogen, preferably bromine, and a liquid carboxylic acid in the presence of a inert organic solvent.

This process is usually conducted in the course of about 4 to 36 hours, preferably about 18 to 24 hours at temperatures in the range of about 0 to 100 ° C, preferably about 20 to 30 ° C, using 1.0 up to 10.0, preferably 1.0 to 1.1 mole, halogen per mole of the compound of the formula 5. Suitable liquid carboxylic acids which can be used are, for example, acetic acid, propionic acid, butyric acid, formic acid and the like. 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, eg diethyl ether, dimethyl sulfoxide, dimethylformamide and the like, 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 V can be prepared by the process shown schematically in Figure 2, wherein R 1 - represents lower alkyl, aryl (e.g. phenyl) or arylalkylene (e.g. benzyl), and Z ', Y and X represent the have the above meaning.

This process can be conveniently carried out by contacting a compound of the formula 7 with a compound 40 of the formula 8 and a strong base, preferably in an inert organ 8401878. "ί. »5 nic solvent.

This process is usually conducted in the course of about 5 to 36 hours, preferably 18 to 24 hours, at temperatures in the range of about 0 to 100 ° C, preferably 75 to 85 ° C, using about 1.0 to 10.0, preferably 1.0 to 1.2 moles of the compound of the formula 8 per mole of the compound of the formula 7. Usually, about 1.0 to 10.0 moles of base per mole of the compound containing uses the formula 8.

Suitable strong bases which can be used are, for example, alkali metal alkoxide, for example sodium methanolate, sodium ethanolate, potassium ethanolate, sodium hydride, potassium hydride and the like. 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, lower alkanols (eg methanol, ethanol and propanol), tetrahydrofuran, dimethoxyethane, dioxane and the like, and compatible mixtures thereof. Suitably, the alkali metal alkolate is prepared in situ by reacting an alkali metal with an excess of alkanol, which in turn serves as a solvent for the above conversion.

The starting materials of formulas 7 and 8 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 the formula 7 is described, for example, in Org. Syn. Coll., Vol. 1, 107 (1941) and the preparation of the compound of formula 8 is described in Org., Syn. Coll., Vol. 1, 270 (1941).

The compounds of formula I, wherein R 1 and R 3 are each hydrogen, 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 have the above meanings. and R 1 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 7 with the compound of the formula 9 and a strong base (eg sodium methanolate, sodium ethanolate), preferably in an inert organic solvent.

This process usually lasts from 5 to 36 hours, preferably 18 to 24 hours, at temperatures in the range of about 0 8401876. 1 to 6 to 100 ° C, preferably 75 to 85 ° C carried out using about 1.0 to 10.0, preferably 1.0 to 1.2 moles, of the compound of formula 9 per mole of the compound of the formula 7. Suitable inert organic solvents which can be used are, for example, lower alkanols (eg methanol, ethanol, propanol, etc.), tetrahydrofuran, dimethoxyethane, dioxane and the like, 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 the formula 7 with the compound of the formula 8.

The hydroxyesters of the formula 9 are generally known compounds and can be prepared by known methods or obvious modifications thereof (eg, using suitably substituted starting materials).

The compounds of formula I, wherein R 1 is hydrogen and R represents alkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenylalkyl (e.g. - (^ 2 ^ = 0¾), may also suitably be 20 is prepared according to the process shown schematically in Figure 4, wherein R 1 represents alkyl, cycloalkyl, alkoxyalkyl, alkoxy, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenyl and R 1 represents lower alkyl, preferably methyl.

This process can be conveniently carried out by contacting the compound of formula 11 with a cyclizing agent under reaction conditions, preferably in an inert organic solvent.

This process is usually conducted over about 10 to 120 minutes, preferably about 10 to 30 minutes, at temperatures in the range of about 0 to 200 ° C, preferably about 115 to 120 ° C, using about 1 to 10, preferably 1 to 2, moles of cyclizing agent per mole of the compound of formula 11. Suitable cyclizing agents which can be used are, for example, strong anhydrous acids, for example sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, methanesulfonic acid and of such. Best results are usually obtained using anhydrous sulfuric acid. Suitable inert organic solvents which can be used are, for example, acetic acid, propionic acid, butyric acid, toluene, xylene and the like, and compatible mixtures thereof.

8401876, "£ 7

The starting materials of the formula II can be prepared according to the process schematically shown in Fig. 5, in which R ™ and R ^ ® have the above meaning, X 'represents chlorine, bromine or iodine and M and Mf independently of each other sodium or lithium.

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

In the first step of this method, the compound of formula 13 is contacted with a non-nucleophilic base, preferably in an inert organic solvent. This step is usually carried out over a period of about 1/2 to 3 hours at temperatures in the range of about 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 13. Suitable non-nucleophilic bases which can be used are, for example, alkali metal hydrides, for example sodium hydride, potassium hydride, etc .; alkali metal amides, for example, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium diethylamide, lithium diisopropylamide, sodium dimethylamide and the like. Sodium hydride is generally preferred because it gives very good results and it is readily commercially available ie. * The alkali metal amides and also natural alkali metal hydrides are generally known compounds and can be prepared by obvious modification thereof 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, diisopropyl ether and the like, and compatible mixtures thereof.

The second step can be carried out by contacting the compound of formula 14 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 about 1 to 4 hours at temperatures ranging from about -78 to 0eC using about 1 to 2, preferably 1 to 1.3 mole equivalents of alkyl base per mole of the compound with formula 8401876 "I * 4 8. Suitable alkyl bases which can be used are, for example, alkali metal alkyls, alkyl Grignard reagents and the like. Preferably lithium n-butyl is used because it gives good results and is easy to trade Suitable solvents that can be used include the solvents listed above with respect to the first stage and the like.

The third step can be carried out by contacting the compound of formula 15 with the appropriate R '' halide, which contains the desired R '' group, preferably in an inert organic solvent. The third stage is also usually carried out in situ with the second stage reaction mixture.

The third step of this process is usually carried out in the course of about 1 to 18 hours, preferably 1 to 5 hours, at temperatures in the range of about -30 to + 30 ° C, preferably 22 to 25 ° C, using about 1 to 10 moles, preferably 1 to 1.5 moles, R'1'X 'per mole of the compound of formula 15. Suitable inert organic solvents include the above solvents, which relate to the first stage of this process 20, and the like. The halides, R '' X ', are generally known compounds and can be prepared by known methods or obvious modifications thereof (e.g. replacement with suitable reaction components and solvents).

The starting materials of the formula (13) can be prepared by the process shown schematically in Figure 6, wherein R 1 represents lower alkyl (preferably methyl) and R 1, X and Y have the above meanings.

This process can be conveniently carried out by contacting the compound of the formula 7 under reaction conditions with the compound of the formula 16 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 5 except that the reactant of the formula 16 is used instead of the reactant of the formula 8. The reactants of formula 16 are simple alkyl alkoxyacetate esters, for example, methyl methoxy acetate. The preparation of such compounds is well known in the art.

40 The compounds of formula 1, in which one or both of R1 and 8401876 τ * * A ..

9 may be substituted by alkylation of the amino group of the corresponding compounds of formula 10, as indicated in the reaction scheme of Fig. 7, wherein R, R *, X and Y have the above meanings and R 4 ' as defined for R25, except hydrogen, R25 is an alkylating agent with the required residue R ^ or a required residue R *, if dialkylation is desired.

This process can be carried out by contacting the compound of formula 10 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 (10) with R 1 iodide or bromide, preferably in an inert organic solvent and preferably in the presence of an acid binding base. This process is usually conducted in the course of about 1.0 to 72.0, preferably 2.0 to 18.0 hours at temperatures within the range of about 0 to 100 ° C, preferably 20 to 45 ° C. If a monoalkylation is desired, usually about 1.0 to 1.1 moles of the R * halide reactant per mole of the compound of formula 10 are used. If it is desired to alkylate both amino hydrogen atoms, usually about 1.9 to 4.0 moles of R 2 halide per mole of the compound of Formula 10 are used. Where it is desired to prepare a compound in which R 1 is alkoxyalkyl or alkylthioalkyl, it is preferable to use a large excess of R 4 halide even if a monoalkylation is desired, for example 3 to 6 moles R 2 "Z1" per mole of the compound of formula 10. Further alkylation can be carried out in a second step if desired. Also variations in r! and are accomplished by first alkylating only one of the two amino hydrogen atoms and then alkylating the second amino hydrogen atom with an alkylating agent having a different R group. The compounds in which R1 and together with the amino nitrogen atoms form a saturated heterocyclic ring can be prepared using the required Z * - (0¾) 2.5-2M, wherein ZM is Cl or Br, as the alkylating agent. The unsaturated R 1 R 3 N heterocyclic ring can be prepared using the required cis-alkenyl dihalide, which contains one of the halogen atoms on each alkenyl carbon atom. Suitable inert organic solvents which can be used are, for example, liquid halogenated alkanes, for example dichloromethane, carbon tetrachloride or dichloroethane, while tetrahydrofuran and the like are also useful. Suitable acid-binding bases which can be used are, for example, the bases described above with respect to the reaction of the compound of the formula 7 with the compound of the formula 8 (Fig. 2).

The compounds of formula 17, wherein lower alkyl represents (for example methyl) and R 1 represents hydrogen or lower alkyl, are advantageously prepared using a dialkyl sulfate as an alkylating agent. This can be conveniently accomplished by contacting a compound of the formula 1 wherein one or both of R1 and / or R110 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 about 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. Mostly an excess of about 2.5 moles of base is used. Preferably, this process is also performed in an inert solvent, such as, for example, dichloromethane, carbon tetrachloride, dichloroethane, tetrahydrofuran and the like.

Suitable strong bases which can be used are, for example, sodium hydroxide, potassium hydroxide, sodium ethanolate, sodium carbonate, potassium carbonate and the like. Suitable phase transfer agents are agents which transfer hydrophilic ions to a lipophilic organic medium and include, for example, benzyl triethyl ammonium chloride, tetra-n-butylammonium chloride, methyl tribtyl ammonium chloride and the like.

The compatible salts of the formula I can be prepared by conventional methods, for example, by treating the compound of the formula 1 wherein R1 and / or R1 are hydrogen with a suitable strong base such as, for example, n. butyl lithium, sodium hydride, potassium hydride and the like which has the desired cation by conventional methods for obtaining the corresponding R1 and / or R1 cationic salts. The enolate salts can be prepared by treating the R 1 and / or R 2 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 preferred to separate the products in question before proceeding to the next step in the reaction process, except for the 8401876. * 11 trap in which the next stage is described as an in-situ stage or is expressly stated otherwise. 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 performed under pressures of about 300 to 3,000 mm Hg and suitably under atmospheric or prevailing pressure.

It will also be appreciated that if typical or preferred operating conditions (eg reaction temperature, times, molar ratios of reactants, solvents, etc.) are stated, other operating conditions could also be used. Optimal reaction conditions (eg, 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 conventional 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:

The term "lower alkyl" denotes both straight and branched alkyl groups having a total of 1 to 4 carbon atoms and includes primary, secondary and teriary alkyl groups. Typical examples of lower alkyls are, for example, methyl, ethyl, n.propyl, isopropyl, n.butyl, tert-butyl.

The term "alkylene" denotes both straight and branched chain alkylene groups and includes, for example, -CH2 "; -CH2 -CH2"; CH013 -CH2CH2 and the like.

The term "lower alkenyl" denotes alkenyl groups of 2 to 6, preferably 2 to 4, carbon atoms, and includes, for example, vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-methylprop-1-enyl and the like.

The term "lower alkoxy" denotes the residue -OR *, wherein R 1 is lower alkyl.

The term "lower alkylthio" denotes the group -SR 'wherein R' is lower alkyl.

The term "lower alkoxyalkyl" denotes the residue R'OR "- wherein R 'and R" are independently straight or branched chain alkyl groups of 1 to 3 carbon atoms.

The term "lower alkylthioalkyl" denotes the residue R'SR "- wherein R 'and R" are independently straight or branched chain alkyl groups of 1 to 3 carbon atoms.

The term "lower alkoxycarbonylalkyl" denotes the remainder

II

R'OCR '' - in which R 'represents lower alkyl and R "represents alkylene of 1 to 4 carbon atoms and are straight or branched chins. Typical alkoxycarbonyl alkyl groups are, for example, -01 ^ 0 (0) 00¾, 20 -CH ( CH3) C (0) 0C2H5 and the like.

The term "halogen" refers to the group of fluorine, chlorine, bromine and iodine.

The term "lower haloalkyl" denotes haloalkyl groups having 1 to 4 carbon atoms and 1 to 3 halogen atoms, which are independently selected from the group: fluorine, chlorine, bromine and iodine. Preferably the lower haloalkyl group has 1 or 2 carbon atoms.

The term "lower haloalkoxy" denotes "lower alkoxy groups" which have 1 to 3 halogen atoms independently selected from the group: fluorine, chlorine, bromine or iodine.

The term "aryl" denotes aryl groups of 6 to 10 carbon atoms and includes, for example, phenyl, naphthyl, indenyl. Typically, the aryl group will be phenyl or naphthyl, because compounds with such groups are more readily available commercially than other aryl compounds.

The term "substituted aryl" denotes aryl groups having 1 to 3 substituents independently selected from the group: lower alkyl, lower alkoxy, halogen, nitro or haloalkyl of 1 to 3 carbon atoms and 1 to 3 halogen atoms. Typical examples of substituted aryl groups are 2-fluorophenyl, 2-chlorophenyl, 2,6-dimethylphenyl, 4-fluorophenyl, 2-methylphenyl, 2-chloro-3-chloro-40 methylphenyl, 2-nitro-5-methylphenyl, 2 , 6-dichlorophenyl, 3-trifluorom-8401876 t * Jr, 13 thylphenyl, 2-methoxyphenyl, 2-bromo-naphth-1-yl, 3-methoxyinden-1-yl and the like.

The term "arylakylene" denotes the residue ArRp-, wherein Ar represents aryl and R 2 represents alkylene of 1 to 3 carbon atoms and includes both straight and branched chain alkylenes, for example methylene, ethylene, 1-methyl ethylene and propylene.

The term "(substituted aryl) -alkylene" or "ring-substituted arylalkylene" denotes the residue Ar * R2- wherein Ar * represents substituted aryl and R2 represents alkylene as defined with respect to arylalkylene.

The term "saturated nitrogenous heterocyclic ring" as used herein with respect to R 1 and R 2 in formula 1 denotes residues of formula / * h 2? ƒ% XCH2) n where η is 1, 2 or 3.

The term "unsaturated nitrogenous heterocyclic ring", as used herein with reference to R 1 and R 2 in Formula 1, denotes groups of formulas 18 to 25.

The term "compatible salts" denotes salts that do not significantly alter the herbicidal properties of the base compound. Suitable salts include cationic salts such as, for example, the cationic salts of lithium, sodium, potassium, alkaline earth metals, ammonia, quaternary ammonium salts and the like.

The term "room temperature" or "ambient temperature" indicates about 20-25 ° C.

The compounds of formula 1 exhibit both pre-emergent and post-emergent herbicidal activity and exhibit particularly good pre-emergent herbicidal activity.

For post-emergent applications, the herbicidal compounds are generally applied directly to the foliage or other plant parts. For pre-emergent applications, the herbicidal compounds can be applied to the growth medium or expected growth medium for the plant. The optimum amount of the herbicidal compound or composition will vary depending on the particular plant species and, if so, the degree of plant growth and the particular portion of the plant to be contacted, and the degree of contamination. 14 tact. The optimal dosage can also vary with the general place or environment (e.g. sheltered places, such as greenhouses compared to open places, such as fields) and the desired type and degree of control. In general, the compounds of the invention are applied in amounts of about 0.02 to 60 kg / ha, preferably about 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 (that) 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. Typically, the composition contains about 0.05 to 95% by weight of the compound of formula 1 or mixtures thereof. Also, concentrates of high concentrations can be prepared which are intended to be diluted before use. The carrier can be a solid, liquid or aerosol. The actual composition may be in the form of granules, powders, dusts, solutions, suspensions, aerosols and the like.

Suitable solid carriers which can be used are, for example, natural clays (such as kaolin, attapulgite, montmorillo staple, etc.), talken, pyrophyllite, diatomaceous earth, synthetic fine silicon dioxide, calcium aluminum silicate, tricalcium phosphate and the like. Also organic materials such as walnut husk flour, cotton seed husks, wheat flour, wood flour, wood bark flour and the like can be used as carriers. Suitable liquid diluents which can be used are, for example, water, organic solvent (for example, hydrocarbons, such as benzene, toluene, dimethyl sulfoxide, kerosene, diesel oil, fuel oil, petroleum naphtha, etc.) and the like. Suitable aerosol carriers which can be used include conventional aerosol carriers such as halogenated alkanes, etc.

The compositions may also contain various promoters and surfactants which favor the transport rate of the active compound in the piat tissue, such as, for example, organic solvents, wetting agents and oils, and in the case of preparations intended for spouts to be used, means which reduce the leachability of the compound 8401876. * * *.

15 or otherwise promote stability in the soil.

The compositions 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 respect to the herbicidal compositions 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 in total about 0.005 to 90 wt.% Of the compound (s) of formula 1, depending on whether the composition is for direct application or to be diluted first.

A better understanding of the invention can be obtained by the following non-limiting examples. Unless expressly stated otherwise, all temperatures and temperature ranges are expressed in degrees Celsius and the term "ambient" or "room temperature" designates about 20 to 25 ° C. The term "percent" or "Z" designates weight percent and the term "mole" denotes graramolecules. The term "equivalent" denotes an amount of reagent, which in moles is equal to the number of moles of the reactant listed in the respective example, before or after expressed as finite number of moles or finite weight or volume. If stated, the magnetic proton nuclear magnetic resonance (NMR) spectrum is determined at 60 MHz, the 35 signals being 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.

8401876 «« * * 16

EXAMPLES

Example I

(3-T rifluoromethylphenyl) - benzylcarbonylacetonitrile

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 about 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 a pH of about 1 with aqueous 10% by weight 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 yield 22.6 g of the title compound.

Likewise, by adapting the above procedure and using the appropriately substituted phenylacetonitrile and ethyl-substituted phenylacetate as starting materials, the following compounds can be prepared: (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- (4-fluorobenzylcarbonyl) -acetonitrile; (3-trifluoromethylphenyl) -1-naphthylmethylene racetonitrile; (2-chloro-3-methylphenyl) -benzylcarbonyl-acetonitrile; (4-ethyl-3-methylphenyl) -benzylcarbonyl-acetonitrile; (5-methoxy-3-chlorophenyl) -benzylcarbonyl-acetonitrile; (3-iodophenyl) -benzylcarbonyl-acetonitrile; (3-difluoromethylthiophenyl) -benzylcarbonyl-acetonitrile; (3-trifluoromethylthiophenyl) -benzylcarbonyl-acetonitrile; (3,5-diethoxyphenyl) benzylcarbonyl acetonitrile; 40 (3-bromophenyl) - (2-nitrobenzylcarbonyl) acetonitrile; (2-chloro-3-methylphenyl) -benzylcarbonyl-acetonitrile; 8401876 * * 17 (3-bromo-2-ethyl-enyl) -naphth-1-ylmethylene-carbony-1-acetone-vibrate; (2,3-dimethylphenyl) -fJ-naphth-1-ylmethyl carbonyl-acetoni trill; (3-chlorophenyl) -benzylcarbonyl-acetonitrile; (3-methylphenyl) -benzylcarbonyl-acetonitrile; 5 (3-tert-butoxyphenyl) -benzylcarbonyl-acetonitrile; (3-propylphenyl) -benzylcarbonyl-acetonitrile; (3-broof enyl) -benzylcarbonyl-ace toni trill; (3-iodophenyl) - (3-nitrobenzylcarbonyl) -acetonitrile; (3-trifluoromethyl-enyl) - (2,3-dichlorobenzylcarbonyl) -ace toni trill; 10 (3-methoxyphenyl) -1-naphthylmethylenecarbonyl acetonitrile; (3-trifluoromethyl) - (3-chloro-8-fluoro-naphth-1-ylmethylenecarbonyl) -acetitrile; (3-Trifluoromethyl) - [(2-Trifluoromethyl-3-methyl-8-methoxy-naphth-1-yl) -ethylenecarbonyl] -acetonitrile; (3-trifluoromethyl) - (inden-1-ylmethylenecarbonyl) -acetonitrile; and (3-trifluoromethyl) - (2-fluoroinden-1-ylmethylenecarbonyl) acetoni trill.

Example II

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

In this example, a solution which resumed 21.8 g of (3-trifluoromethyl-20-phenyl) -benzylcarbonyl-acetonitrile dissolved 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 give 8.4 g of a white solid which was dried to yield 7.0 g of the title compound.

Likewise, by adapting the above protocol to the compounds listed in Example I, the following compounds can be prepared: 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-dihydro-furan; 2-phenyl-3-ox 0-4- (2-bromo-3-trofluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (6-fluoro-3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 40 2-phenyl-3-oxo-4- (4-methyl-3-trifluoromethylphenyl) -5-amino-2,3-dihydro 8401876. - * 18 furan; 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-dihydro-5 furan; 2-phenyl-3-oxo-4- (3,5-di-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; 2-phenyl-3-oxo-4- (3-difluoromethoxyphenyl) -5-araino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-trifluoromethoxyphenyl) -5-amino-2,3-dihydrofuran; 2- (4-fluorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro-10 furan; 2- (1-naphthyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; 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-dihydro furan; 2-phenyl-3-oxo-4- (5-methoxy-3-chlorophenyl) -5-amino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-iodophenyl) -5-amino-2,3-dihydro furan; 2-phenyl-3-oxo-4- (3-di-fluoromethyl-thio-phenyl) -5-amino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-amino-2,3-dihydro furan; 2-pheny 1-3-oxo-4- (3,5-diethoxyphenyl) -5-amino-2,3-dihydrofuran; 2- (2-nitrophenyl) -3-oxo-4- (3-bromophenyl) -5-amino-2,3-dihydro furan; 2-phenyl-3-oxo-4- (2-chloro-3-methylphenyl) -5-amino-2,3-dihydrofuran; 2- (1-naphthyl) -3-ox 0-4 - (3-bromo-2-ethylphenyl) -5-amino-2,3-dihydro furan; 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-dihydro furan; 2-phenyl-3-oxo-4- (3-methylphenyl) -5-amino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-butoxyphenyl) -5-amino-2,3-dihydro furan; 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-dichlorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-di-30 hydrofuran; 2- (1-naphthyl) -3-oxo-4- (3-methoxyphenyl) -5-amino-2,3-dihydrofuran; 2- (3-chloro-8-fluoro-naphthyl-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; 2- (2-trifluoromethyl-3-methyl-8-methoxy-naphth-1-yl) -3-oxo-4- (trifluoro-35 methylphenyl) -5-amino-2,3-dihydrofuran; 2-inden-1-y 1-3-oxo-4- (3-trofluoromethylphenyl) -5-amino-2,3-dihydro furan; and 2- (2-fluoroinden-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran.

8401876 *

X

»19

Example III

2-Me thy 1-3-oxor-4- (3-trifluorom thy If eny 1) -5-amlno-2,3-dihydr or ur an

100 ml of methanol were placed in a 500 ml dry three-necked round bottom flask equipped with a mechanical stirrer, a dropping funnel and a reflux condenser. 3.5 g of natrim were added to the stirred solvent. After all the metal had dissolved, a solution of 13.0 g of ethyl L - (+) - lactate and 18.5 g of m-trifluoromethylphenylacetonitrile in 30 ml of ethanol was added dropwise to the reaction mixture. The mixture turned dark red and after the addition was completed, the mixture was refluxed overnight (about 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 about 1). The mixture was then extracted with 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 aliquots of crystals were collected to give a total of 4.7 g of the title compound.

Likewise, by adapting the above protocol and using the corresponding starting substituted corresponding materials, the following compounds can be prepared: 2-ethyl-3-ox 0-4- (3-trifluoromethylphenyl) - 5-amino-2,3-dihydrofuran; 2-th thy 1-3-oxo-4- (5-chloro-3-trifluoromethyl-phenyl) -5-amino-2,3-dihydrofuran; 2-cyclopentyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; 2-vinyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2-allyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; 2-allyl-3-oxo-4- (2-methoxy-3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2-trifluoromethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro-furan; 2-methyl-3-oxop-4- (3-difluoromethoxyphenyl) -5-amino-2,3-dihydro furan; 2-methyl 1-3-oxo-4- (3-trifluoromethoxyphenyl) -5-amino-2,3-dihydrofuran; 2- (2-chlorovinyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 40 2- (2-chlorovinyl) -3-oxo-4- (5-propoxy-3-trifluoromethylphenyl) -5-amino-2,3-dihydrofiran; 8401876 20 2-methyl-3-oxo-4- (2-methoxy-3-chlorophenyl) -5-amino-2,3-dihydro furan; 2-ethyl-3-oxo-4- (2-chloro-3-fluorophenyl) -5-amino-2,3-dihydrofuran; 2-vinyl yl-3-oxo-4 - (3-methyl-4-methoxyphenyl) -5-amino-2,3-dihydro furan; 2-all-yl-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-dihydro furan; 2-methyl-3-oxo-4- (3-difluoromethylthiophenyl) -5-amino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-amino-2,3-dihydro furan; 2-ethyl-3-oxo-4- (3-chlorophenyl) -5-amino-2,3-dihydrofuran; 2-vinyl-3-oxo-4- (3-methylphenyl) -5-amino-2,3-dihydro furan; 2- all yl-3-oxo-4- [3,5-di- (trifluoromethyl) phenyl] -5-amino-2,3-dihydro-furan; 2-trifluoromethyl-3-oxo-4- (4-fluorophenyl) -5-amino-2,3-dihydro furan; 2- (2-chlorovinyl) -3-oxo-4- (2-bromophenyl) -3-oxo-5-amino-2,3-dihydrofuran; 2-propyl-3-oxo-4 - (2-methoxy-3-chlorophenyl) -5-amino-2,3-dihydro furan; 2-butyl-3-oxo-4- (2-chloro-3-fluorophenyl) -5-amino-2,3-dihydrofuran; 2-vinyl-3-ox 0-4- (3-chloro-4-methoxyphenyl) -5-amino-2,3-dihydro furan; 2- all yl-3-oxo-4- (3-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-dihydro furan; 2-methyl-3-oxo-4- (3,5-difluorophenyl) -5-amino-2,3-dihydrofuran; 2-vinyl-3-oxo-4- (3,5-diethylphenyl) -5-amino-2,3-dihydro furan; 2-ally 1-3-OXO-4- (3-propoxyphenyl) -5-amino-2,3-dihydrofuran; 2-trifluoromethyl-3-oxo-4- (3-fluorophenyl) -5-amino-2,3-dihydro furan; 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-dihydro furan; 2-benzy 1-3-oxo-4- (2-isopropoxy-3-trifluoromethyl-phenyl) -5-amino-2,3-d-1-35 hydrofuran; 2- (3-chlorophenyl) -3-oxo-4- (2,3-dimethylphenyl) -5-amino-2,3-dihydro furan; 2-naphth-1-yl-3-oxo-4- (3-trifluoromethyl-1-4-bromophenyl) -5-amino-2,3-dihydro furan; 2- (3-methylphenyl) -3-oxo-4- (3-butyl-4-methylphenyl) -3-oxo-5-amino-2,3-40 dihydrofuran; 84 0 1 8 7 6 * 21 2- (3-fluorophenyl) -3-oxo-4- (3-chlorophenyl) -5-amino-2,3-dihydro furan; 2- (2,3,5-trifluorophenyl-3-oxo-4- (3-trifluoromethylphenyl> -5-amino-2,3-dihydrofuran; 2- (3-methylnaphth-1-yl) -3-oxo-4 - (trifluoromethylphenyl) -5-amino-2,3-di-5-hydrofuran; 2- (2'-chlorovinyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran ; 2-fluoromethyl-3-oxo-4- (trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2-methoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihy -10 drofuran; 2-propoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2-ethoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 15 2- (2-methoxypropyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- methylthiomethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; and 2- (1-propylthioethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino- 2,3-di-20 hydrofuran.

Example IV

(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, resulting in 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 varase phase was acidified with aqueous 10% hydrochloric acid to a pH of about 1 and extracted three times with diethyl ether. The diethyl ether extracts were combined, washed twice with 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.

Likewise, by adapting the above 8401876, 1 '22 protocol, but using other (substituted and disubstituted phenyl) acetonitriles instead of the (3-trifluoromethylphenyl) acetonitrile, the corresponding substituted and disubstituted substituted phenyl analogs of the title compound are prepared.

5 Example V

(3-Trifluoromethyl-phenyl) -2-flethoxy-isovaleryl-acetonitrile

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 about 0 ° C under a nitrogen atmosphere, resulting in hydrogen evolution . After no more hydrogen evolution was observed, the mixture was cooled to about -78 ° C and 24.3 ml of 1.6 M n-butyl lithium in hexane were added dropwise. The mixture was stirred at -78 ° C for 1½ hours and then at about 0-4 ° C for an additional 20 minutes. After that, 3.9 ml (about 6.64 g) of 2-iodopropane were added dropwise and the mixture was stirred overnight (about 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.

Likewise, by using the same protocol but using the appropriate alkyl, aryl, or substituted aryl iodide, bromide, or chloride instead of iodopropane, the following compounds can be prepared: (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] -35 acetonitrile; (3-trifluoromethylphenyl) - [2-methoxy-3- (2-chloro-3-propylphenyl) propionyl] acetonitrile; (3-Trifluoromethylphenyl) - [2-methoxy-3- (2-nitro-3-methoxyphenyl) propionyl] acetonitrile; 40 (3-Trifluoromethylphenyl) - [2-methoxy-3- (2-fluoro-3-21,2'-dichloroethylphene-8401876 23 n yl) propionyl] acetonitrile; (3-trifluoromethylphenyl) - [2-methoxy-3- (2,3-dichloro-6-methylphenyl) propionyl] acetonitrile; (3-trifluoromethylphenyl) - (2-methoxy-4-phenylbutyryl) acetonitrile; 5 (3-trifluoromethylphenyl) - [2-methoxy-5- (2-bromophenyl) valeryl] acetonitrile; (3-trifluoromethylphenyl) -2- (2-methoxy-3-methyl-4-phenylbutyryl) acetonitrile; (3-trifluoromethyl) - (2-methoxy-3-naphth-1-yl-propionyl) acetoni trill; (3-trifluo methyl) - [2-methoxy-3- (2-fluoro-naphth-1-yl) propionyl] acetoni-10 trill; (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-nitronaphthl-yl) propionyl] acetonitrile 15 (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-20 1-yl) propionyl] acetonitrile; (3-trifluoromethyl) -2- (2-methoxy-4-naphth-1-ylbutyryl) acetonitrile; (3-trifluoromethyl) - [2-methoxy-5- (8-fluoro-naphth-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.

Likewise, by adapting the above protocol and using other (mono- or bi-substituted phenyl) (methoxyacetyl) acetonitriles instead of the (3-trifluoromethylphenyl) - (2-methoxyacetyl) acetonitrile, the corresponding mono- or bi-substituted phenyl derivatives of the above compounds are prepared.

Example VI

2-Isopropyl-3-oxo-4- (3-trifluoromethyl-phenyl) -5-amino-2,3-dihydrofuran. In this example, a mixture containing 11.4 g (3-trifluoromethyl-phenyl) - (2- methoxylsovaleryl) acetonitrile and 7.8 g of concentrated sulfuric acid in 50 ml of acetic acid, heated to reflux for 30 minutes and then concentrated by evaporation in vacuo. The 3401278 4 24 concentrate was mixed with diethyl ether, washed three times with 1N aqueous sodium hydroxide, dried over magnesium sulfate and concentrated by evaporation to yield an oil. The oil was triturated in 20% (volume) ethyl acetate: 80% petroleum ether and left overnight (14-16 hours). The solid 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.

Likewise, using 3-trifluoromethylphenyl-dimethoxyacetyl-acetonitrile, which can be prepared according to the procedure of Example I, and the other compounds indicated in Example V as products, the following compounds can be prepared: 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-trifluoromethyl-phenyl) -5-amino-2,3-dihydro-furan; 2- (3-methylbenzyl) -3-oxo-4- (3-trifluoromethyl-phenyl) -5-amino-2,3-dihydrofuran; 2- (2-ethoxybenzyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2 "(3-nitrobenzyl) -3-oxo-4- (3" trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (4-fluorophen and yl) -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- (0-phenethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofu-35 ran; 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; 40 2-naphth-1-ylmethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-di-8401876 *. . Hydrofuran; 2- (2-fluoroaft-1-yimethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (3-butylnaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-5 2,3-dihydrofuraa; 2- (5-methoxynaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuraa; 2- (6-nitronaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (7-Trifluoromethylnaphth-1-ylmethylene) -3-axo-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-fluoromethyl-naphth-1-yl) -3-oxo-4- (3-trifluoromethyl-15-phenyl) -5-amino-2,3-dihydrofuran; 2- (0-naphth-1-ylethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydro furan; 2-f-0- (8-fluoro-t-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-dihydrofuraa; 2-iadea-1-ylmethylea-3-oxo-4- (3-trifluoromethylpheayl) -5-amino-2,3-dihydro furan; and 2- (2-fluoroinden-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-ami-25-no-2,3-dihydrofuran.

Likewise, by adapting the above protocol using the corresponding mono and di-substituted analogs of the starting material for the above compounds, the corresponding 4- (3-methylphenyl) -; 4- (3-g-fluoro-30 ethoxyphenyl) -; 4- (3-difluoromethylthiophenyl) -; 4- (3-chlorophenyl) -; 4- (2-Bromo-3-trifluoromethylphenyl) - and 4- (2-methyl-3-difluoromethylthio-phenyl) analogues of the above compounds are prepared.

Example VII

2-Phenyl-3-oxo-4- (3-trifluoromethyl-phenyl) -5-methylamino-2,3-dihydrofuran 35 In this example, prepare approximately 1 g of solid sodium hydroxide in 4.0 ml of water added to a mixture of 3 g 2-phenyl-3-oxo-4- (3-trifluoromethyl-phenyl) -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 biphasic mixture was stirred at room temperature for about 2 hours and then washed three times with water three times, dried over magnesium sulfate and then concentrated in vacuo. The residue was then purified by silica gel chromatography, eluting with mixtures of tetrahydrofuran and chloroform to afford the title compound 5.

Likewise, by adapting the above procedure using the products listed in Examples II, III and VI as starting materials, the corresponding 5-methyl-amino homologues thereof can be prepared, 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-di-15 hydrofuran; 2-phenyl-3-oxo-4- (6-fluoro-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-trifluoromethylphenyl) -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-dihydro-furan; 2-phenyl-3-oxo-4- (3-difluoromethoxyphenyl) -5-methylamino-2,3-dihydro furan; 2-f and yl-3-oxo-4- (3-trifluoromethoxyphenyl) -5-methylamino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-methylamino-2,3-dihydro-furan; 2- (4-fluorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (1-naphthyl) -3-oxo-4- (3-trifluoromethyl-phenyl) -5-methylamino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (2-chloro-3-methylphenyl) -5-methylamino-2,3-dihydro furan; . 2-phenyl-3-oxo-4- (4-ethyl-3-methylphenyl) -5-methylamino-2,3-dihydro furan; 2-phenyl-3-oxo-4- (5-methoxy-3-chlorophenyl) -5-methylamino-2,3-dihydrofuran; 40 2-phenyl-3-oxo-4- (3-iodophenyl) -5-methylamino-2,3-dihydro furan; 84 0 1 8 7 6 27 2-phenyl-3-oxo-4- (3-difluoronethyltMophenyl) -5-methylamino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-trifluoromethylthio phenyl) -5-methylamino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3,5-diethoxyphenyl) -5-methylamino-2,3-dihydro furan; 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-dihydro-10 furan; 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-dihydro furan; 2-phenyl-3-oxo-4- (3-methylphenyl) -5-methylamino-2,3-dihydrofuran; 2-phenyl-3- * ooxo-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-dihydro furan; 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-dihydro furan; 2- (3-chloro-8-fluoro-naphth-1-yl) -3-oxo-4- (3-trifluoromethyl-phenyl) -5-methyl-1-amino-2,3-dihydrofuran; 2- (2-Trifluoromethyl-3-methyl-8-methoxynaphth-1-yl) -3-oxo-4- (3-trifluoromer-25-ylphenyl) -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-Qxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (3-trifluoromethyl-phenyl) -5-methylamino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (5-chloro-3-trifluoromethyl-phenyl) -5-methylamino-2,3-dihydrofuran; 2-cyclopentyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-vinyl-3-oxo-4- (3-trifluoromethyl-phenyl) -5-methylamino-2,3-dihydrofuran; 2-allyl-3-oxo-4- (3-trifluoromethyl-phenyl) -5-thylamino-2,3-dihydrofuran; 2-allyl-3-oxo-4- (2-methoxy-3-trifluoromethylphenyl) -5-methylamino-2,3-di-40 hydrofuran; 6 4 ö 1 3 7 8 28 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-10-2,3-dihydrofuran; 2-methyl-3-oxo-4- (2-methoxy-3-chlorophenyl) -5-methylamino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (2-chloro-3-fluorophenyl) -5-methylamino-2,3-dihydro furan; 2-vinyl-3-oxo-4- (3-methyl-4-methoxyphenyl) -5-methylaraino-2,3-dihydroflu-15 ran; 2-allyl-3-oxo-4- (3,6-dimethylphenyl) -5-methylamino-2,3-dihydrofuran; 2 "trifluoromethyl-3-oxo-4- (3-trifluoromethyl-4-brooniphenyl) -5-methylamino-2,3-dihydro furan; 2- (2-chlorovinyl) -3-oxo-4- (3-nitro-4-methylphenyl) -3-oxo-5-methylamino-20 2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-methoxyphenyl) -5-methyl amino-2,3-dihydrofuran; 2-methy 1-3-oxo-4- (3-difluoromethyl thiophenyl) -5-methylamino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-methylamino-2,3-dihydro-furan; 2-ethyl-3-oxo-4- (3-chlorophenyl) -5-methylamino-2,3-dihydro furan; 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-Trifluoromethyl-3-oxo-4- (4-fluorophenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-chlorovinyl) -3-oxo-4- (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-dihydro furan; 2-trifluoromethyl-3-oxo-4- (3-trifluoromethyl-5-bromophenyl) -5-methyl-40 amino-2,3-dihydrofuran; 8401876 *, β 29 2 - (2-chlorovinyl) -3-οχο-4- (3-fluoro-4-methylphenyl) -3-oxo-5-methylamino-2,3-dihydro furan; 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-dihydro furan; 2-allyl-3-oxo-4- (3-propoxyphenyl) -5-methylamino-2,3-dihydrofuran; 2-Trifluoromethyl-3-oxo-4- (3-fluorophenyl) -5-methylamino-2,3-dihydro furan 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-dihydro furan; 2-benzyl-3-oxo-4- (2-isopropoxy-3-trifluoromethyl-phenyl) -5-methylamino-2,3-dihydrofuran; 2- (3-chlorophenyl) -3-oxo- (2,3-dimethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-naphth-1-yl-3-oxo-4- (3-trifluoromethyl-4-bromophenyl) -5-ethylamino-2,3-15 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-dihydro furan; 2- (2,3,5-Trifluoro-phenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylaniino-2,3-dihydrofuran; and 2- (3-methylnaphth-1-yl) -3-oxo-4- (trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (chlorovinyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-di-25 hydrofuran; 2-fluoromethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydro furan; 2-methoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-ethoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydro furan; 2- (2-methoxypropyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-methyl thiomethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; and 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-di-40 hydrofuran; §4 0 1 C 7 a φ * * 2- (3-methylbenzyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-ethoxybenzyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-nonhylamino-2,3-dihydrofuran; 2- (3-nitrobenzyl) -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-with: hylami-10-no-2,3-dihydrofuran; 2- (2-chloro-3-propylphenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; 2- (2-nitro-3-methoxyphenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; 2- (2-fluoro-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- (g-phenethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-d 1-20 hydrofuran; 2- [3- (2-bromophenyl) propyl] -3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; 2- [1-methyl-2- (phenyl) ethyl] -3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; 2-naphth-1-ylmethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-fluoro-naphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; 2- (3-butylnaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methyl-30-amino-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 (3-trifluoromethylphenyl) -5-methyl-amino-2,3-dihydrofuran; 2- (7-Trifluoromethylnaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-chloro-8-methylnaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (3-methoxy-5-nitro-7-fluoromethyl-naphth-1-yl) -3-oxo-4- (3-trifluoromethyl-40-phenyl) -5-methylamino-2,3-dihydrofuran; & 4 P v, i * * 31 2-methoxy-3-o-xo-4- (3-trifluoromethylphenyl) -5-methylamine-2,3-dihydrofuran; 2- (8-naphth-1-ylethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- [0- (8-Fluoro-naphth-1-yl) ethyl] -3-oxo-4- (3-trifluoromethylphenyl) -5-mer thylamino-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-10 2,3-dihydrofuran; and 2- (2-fluoroinden-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran.

Likewise, by approximately doubling the amount of dimethyl sulfate and extending the reaction time, the corresponding 3-dimethylamino homologs of the above compounds can be prepared. Using corresponding diethyl sulfate instead of dimethyl sulfate, the corresponding 5-ethylamino and 5-diethyl amino homologues of the above compounds can be prepared in the same manner.

Example VIII

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

In 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, followed by addition of 1.44 g of allyl bromide and 0.27 g of benzyl triethyl ammonium chloride. The resulting biphasic mixture was stirred at room temperature for about 18 hours, after which it was washed three times with water, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by silica gel chromatography and eluting with chloroform to give 2.5 g of the title compound.

Likewise, by applying this protocol to the products listed in Examples II, III and VI, the corresponding 5-allylamino analogs thereof can be prepared * Likewise, by approximately doubling the amount of allyl bromide and sodium hydroxide, the corresponding 5- diallylamino analogs thereof are prepared.

Likewise, using ethyl bromide instead of allyl bromide, the corresponding 5-ethylamino and 5-diethyl-40 amino analogs can be prepared.

8401876 t 32

Likewise, by following the same procedure using methoxymethyl bromide, ethyl thiomethyl bromide, methyl bromoacetate, methyl 2-bromobutyrate, 1,5-dibromopentane, respectively. cis-1,4-dibromobut-1,3-diene instead of the allyl bromide the corresponding 5-methoxymethylamino, 5-ethylthiomethylamino, 5-methoxy-carbonylmethylamino, 5- (1-methoxycarbonylpropylamino) -, 5 -piperidine- 1-yl and 5-pyrrole-1-yl derivatives of the products listed in Examples II, III and VI are prepared, for example: 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxymethylamino-2,3-di-10 hydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxyamino-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) -5-ethylthiomethylamino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylphenyl) -5-ethylthiomethylamino-2,3-20 dihydrofuran; 2-ethoxymethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-ethyl thiomethyl-amino-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-methoxycarbonyl-methylmethylamino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxycarbonylmethyl amino-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-methoxycarbonyl prop-1-yl) amino-2,3-dihydrofuran; 2-fluoro-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-methyloxycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-methoxycarbonylprop-1-40 yl) amino-2,3-dihydrofuran; 8401876 * 33 2-Naphth-1-yl-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-methoxycarbonylprop-1-yl) araino-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-pyrrole-1-yl-2,3-dihydrofuran, etc.

Likewise, by applying the above procedures using the 5-methylamino products of Example VII as starting materials, the corresponding 5- (N-methyl-N-allylamino) -, 5- (N-methyl- N-ethylamino) -, 5- (N-methyl-N-methoxymethylamino) -, 5- (N-methyl-N-ethyl thiomethylamino) -, 5 ”(N-methyl-N-methoxycarbonylmethyl-thylamino) - and 5- (N-methyl-N-1-methoxycarbonylpropylamino) analogs are prepared.

Example IX

Lithium salt of 2-phenyl-3-axo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran (R ^ · CH3, R ^ - Li). In this example, 5.4 ml of 1 .6 M n-butyl lithium in hexane added dropwise with stirring to a solution at -30 ° C, containing 2.86 g of 2-phenyl-3-axo-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 Z, H * 3.84 Z, N * 4.13 Z; found: C 61.82 Z, H * 4.90 Z, N e 3.48 Z.

Likewise, using the above procedure, the corresponding lithium salts of the compounds of Examples II-V can also be prepared.

Example X.

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Example VIII

In this example, 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.

Pre-emergent herbicide trial

The pre-emergent herbicidal 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 non-ionic 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 with 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 where some of the compounds at a smaller dose of 15.6 µg / cm 2 were tested. The pot was poured and placed in a greenhouse. The pot was watered intermittently and observed over a 3 week period on seedling sprouting, sprouting seedling health, etc.

At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A scale from 0 to 100 was used, with 0 indicating no phytotoxicity and 30 indicating complete death. The results of these tests are summarized in Table D.

Post-emergent herbicide trial

The compound to be tested was formulated in the same manner as described above for the pre-emergent trial.

35 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 7½ to 10 cm high) (about 15 to 20 plants per pot ), at a dose of 27.5 µg / cm 2. After the plants became dry, they were placed in a greenhouse and. 40 thereafter, if necessary, watered at intervals. The 8401876 43 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 from 0 to 100 was used, with 0 indicating no phytotoxicity and 100 indicating total death. The results of these tests are summarized in Table E.

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As shown in Table D above, the compounds of the invention exhibit a broad spectrum of activity of excellent pre-emergent phytotoxic activity, which is particularly true for compounds Nos 2, 4, 7, 9, 12, 14, 16, 22. In addition, In general, the compounds also exhibit post-emergent phytotoxic activity against broad-leaved plants and in some cases also against grasses, as shown in Table E, particularly with compounds Nos 7, 9, 12, 14, 16 22 and 23. It has also been found that the corresponding comparative compounds have much worse activity than the corresponding compounds of the present invention.

Of course, many modifications and variations of the invention described above and described below are possible without departing from the essence and scope thereof.

8401876

Claims (44)

CONCLUSIONS 1 * Compound of formula 1, wherein R is lower alkyl, cycloalkyl of 3 to 7 carbon atoms, lower alkenyl, haloalkyl of 1 to 4 carbon atoms and 1 to 3 halogen atoms independently selected from the group : fluorine, chlorine, bromine and iodine, haloalkenyl with 2 to 4 carbon atoms and 1 to 3 halogen atoms, which are independently selected from the group: fluorine, chlorine, bromine and iodine, lower alkoxy, lower alkylthio, lower alkoxyalkyl, in which the alkyl and alkoxy radicals independently have 1 to 3 carbon atoms, alkylthioalkyl, wherein the alkyl radicals independently have 1 to 3 carbon atoms, phenyl, naphth-1-yl, inden-1-yl, 4-fluorophenyl, aralkylene having 1 to 3 carbon atoms in the alkylene radical and wherein the aryl radical is phenyl, naphth-1-yl or inden-1-yl, or R represents substituted aryl or substituted arylalkylene selected from the group of formula 2, 3 and 4, where one, two or three of R ^, R ^, R®, R ^, R® and R ^ are independently selected from the group: lower alkyl, lower alkoxy, halogen, nitro or haloalkyl having 1 to 3 carbon atoms and 1 to 3 equal or different halogen atoms, and the remaining hydrogen, and R® being single bond or alkylene of 1 to 3 carbon atoms; R * represents hydrogen or alkyl of 1 to 4 carbon atoms; r 2 hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl or R 1 and R 2 together with the nitrogen atom to which they are attached, a saturated or unsaturated nitrogenous heterocyclic ring having 3 to 6 carbon atoms, one of which is nitrogen and the other being carbon atoms; 30. represents hydrogen, lower alkyl, lower alkoxy, halogen or trifluoromethyl and may be present at any available location on the phenyl ring; and Y lower alkyl, lower alkoxy, halogen, lower haloalkyl of 1 to 4 carbon atoms and 1 to 3 equal or different halogen atoms, lower haloalkoxy of 1 to 4 carbon atoms and 1 to 3 equal 35 or different halogen atoms or lower haloalkylthio of 1 to 4 carbon atoms and 1 to 3 represent the same or different halogen atoms; with the proviso that if Y is halogen, R, R ^ and R ^ are not all hydrogen and further, provided that if Y is any other than trifluoromethyl and X is any other than hydrogen 40 and R and R 1 each are hydrogen, R represents methyl, ethyl, propyl, 2-halo-8401876 * 4-phenyl, 2-lower alkylphenyl or 4-fluorophenyl, and compatible salts thereof. A compound according to claim 1, wherein one of R1 and R2 is hydrogen, methyl, ethyl or propyl. The compound of claim 1, wherein one of R 1 and R 2 is methyl or ethyl and the other is hydrogen, methyl or ethyl. A compound according to claim 1, wherein one of R 1 and R 2 is hydrogen and the other is methyl, ethyl or propyl. A compound according to claim 1, wherein X is hydrogen. A compound according to claim 2, wherein X is hydrogen. A compound according to claim 3, wherein X is hydrogen. A compound according to claim 1, wherein R represents phenyl, naphth-1-yl, 4-fluorophenyl or substituted aryl. The compound of claim 8, wherein R represents phenyl, naphthyl or en-15-substituted phenyl. The compound of claim 9, wherein R represents phenyl, halophenyl or lower alkyl phenyl. A compound according to claim 10, wherein R represents phenyl, 4-fluorophenyl, 2-halophenyl or 2-lower alkyl phenyl. A compound according to claim 11, wherein X is hydrogen and R * and R2 are independently selected from the group: hydrogen, methyl and ethyl. The compound of claim 1, wherein R represents lower alkyl, cycloalkyl, lower alkenyl, haloalkyl or haloalkenyl. The compound of claim 13, wherein one of R 1 and R 2 is hydrogen, methyl or ethyl and the other is methyl or ethyl. A compound according to claim 14, wherein R represents methyl, ethyl or propyl. The compound of claim 15, wherein one of R 1 and R 2 is hydrogen and the other is methyl or ethyl. A compound according to claim 16, wherein X represents hydrogen. A compound of the formula 29, wherein R is lower alkyl, cycloalkyl of 3 to 7 carbon atoms, lower alkenyl, haloalkyl of 1 to 4 carbon atoms, and 1 to 3 halogen atoms independently selected from the group: fluorine, chlorine, bromine and iodine, haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, which are independently selected from the group: fluorine, chlorine, bromine and iodine, lower alkoxy, lower alkylthio, 40 lower alkoxyalkyl, in which the alkyl and alkoxy radicals independently of 84 0 1 8 7 6 each have 1 to 3 carbon atoms, lower alkylthioalkyl, wherein the alkyl radicals independently have 1 to 3 carbon atoms, phenyl, naphth-1-yl, inden-1-yl, 4- fluorophenyl, aralkylene of 1 to 3 carbon atoms in the alkylene radical and wherein the aryl radical is phenyl, naphth-1-5 yl or inden-1-yl, or R is a substituted aryl or substituted arylalkylene selected from the group of formulas 2, 3 and 4, wherein "one, two or three of R ', R? , R ^, r7, R? and R® are independently selected from the group: lower alkyl, lower alkoxy, halogen, nitro and haloalkyl having 1 to 3 carbon atoms and 1 to 3 equal or different halogen atoms, and the remainder being hydrogen, and R 1 a single bond or alkylene of 1 to 3 carbon atoms; R 1 represents hydrogen or alkyl of 1 to 4 carbon atoms; R 1 represents hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl or and R 1, together with the nitrogen atom to which they are attached, a saturated or unsaturated nitrogen-containing heterocyclic moiety of 3 to 6 carbon atoms, of which one is nitrogen and the remaining carbon atoms; X represents hydrogen, lower alkyl, lower alkoxy, halogen or trifluoromethyl and may be present at any available location on the phenyl ring; 25 and compatible salts thereof. A compound according to claim 18, wherein R 1 and R 1 independently represent hydrogen, methyl or ethyl. A compound according to claim 19, wherein one of R 1 and R 1 is methyl or ethyl and the other is hydrogen, methyl or ethyl. The compound of claim 18, wherein one of R 1 and R 1 is methyl or ethyl and the other is hydrogen. A compound according to claim 19, wherein X represents hydrogen and R represents phenyl, naphthyl, 4-fluorophenyl, 2-halophenyl or 2-lower alkyl phenyl. The compound of claim 22, wherein% is one of R * 1 and hydrogen and the other is hydrogen, methyl or ethyl. The compound of claim 23, wherein R represents phenyl, 2-fluorophenyl, 2-chlorophenyl or 2-methylphenyl. The compound of claim 23, wherein R represents phenyl. The compound of claim 23, wherein R represents phenyl and 8401876 * 4 is one of R * and R 2 is hydrogen and the other is methyl. A compound according to claim 23, wherein R represents phenyl and one of R * - and R 1 is hydrogen and the other is ethyl. A compound according to claim 18, wherein R represents lower alkyl, cyclo-5 alkyl, lower alkenyl, lower haloalkyl or lower haloalkenyl. A compound according to claim 28, wherein R 1 independently represents hydrogen, methyl or ethyl. 30. A compound of formula 29, wherein R represents methyl, ethyl or propyl 10. The compound of claim 30, wherein one of R * and R 1 is hydrogen and the other is methyl or ethyl and X represents hydrogen. The compound of claim 29, wherein X represents hydrogen. The compound of claim 18, wherein X represents hydrogen. The compound of claim 1, wherein X represents hydrogen. A compound according to claim 34, wherein Y represents a lower haloalkyl having 1 or 2 carbon atoms. 36. Herbicidal composition consisting of a herbicidally effective amount of a compound according to claim 1 or of a mixture of such compounds and a compatible carrier. Herbicidal composition comprising a herbicidally effective amount of a compound according to claim 25 or mixtures thereof and a compatible carrier. 38. A method of preventing or destroying plants, characterized in that an herbicidally effective amount of a compound according to claim 1 or mixtures thereof is applied to the foliage or potential growth medium of the plants. 39. A method of preventing or destroying plants, characterized in that an herbicidally effective amount of a compound according to claim 25 or mixtures thereof is applied to the foliage or potential growth medium of the plants. A plant growth control agent containing an amount of a compound according to claim 1 or mixtures thereof effective to alter the growth pattern of the plants. 41. A method of controlling the growth of plants, characterized in that an amount of a compound according to claim 1 or mixtures thereof effective on the growth pattern is applied to the foliage of the plants or to their growing medium of such plants. 42. A process for preparing a compound according to claim 8401876 -1 -1 »4 1, wherein R represents phenyl, naphth-1-yl, inden-1-yl or a substituted aryl as defined in claim 1, with characterized in that the corresponding compound of formula 5 wherein X and Y are as defined in claim 1 and Z 'corresponds to the desired aryl-5 or substituted aryl substituent R is contacted with a halogen under reaction conditions from the group consisting of chlorine, bromine and iodine and a liquid carboxylic acid to form the corresponding compound of the formula 1. 43. Process according to claim 42, characterized in that the process is carried out in an inert organic solvent at temperatures in the range from about 0 to 100 ° C and the halogen is bromine. 44. Process according to claim 43, characterized in that an excess of liquid carboxylic acid is used as the inert organic solvent. 1 1] I 1-1 H-H 1-1 · + $ 401876