BE899931A - 5-AMINO-3-OXO-4-PHENYL-2,3-DIHYDROFURANS SUBSTITUTED ON THE RADICAL PHENYL HERBICIDES AND THEIR DERIVATIVES. - Google Patents

Abstract

5-amino-3-oxo-4-phenyl-2,3-dihydrofurans substituted on the phenyl radical and their derivatives of formula (I) which are phytotoxic in pre-emergence and post-emergence and useful as herbicides or, in doses weaker, as regulators of plant growth. Examples of these compounds are 2-phenyl-3-oxo-4- (5-chloro-3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran and 2-phenyl-3-oxo-4- (4 -chloro-3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran.

Description

       

    <EMI ID = 1.1>
 

  
5-Amino-3-oxo-4-phenyl-2,3-dihydrofurans substituted on the phenyl radical herbicides and their derivatives.

  
The present invention relates to derivatives of 5-amino-3-oxo-4-phenyl-2,3-dihydrofuran substituted on the phenyl radical and the use of these compounds as herbicides and regulators of plant growth.

  
An academic article in Chemiker-Zeitung 104 (1980) n [deg.] 10, pages 302-303 describes cyclization

  
  <EMI ID = 2.1>

  
into 5-dimethylamino-2,4-diphenyl-2,3-dihydrofuran. British patent n [deg.] 1,521,092 describes certain 3-phenyl-4 (1H) -pyrid-ones or -thiones 5-substituted as being herbicides. Japanese patent application
13.710 / 69 (Chemical Abstracts 71: 61195e) gives the general formula for 5-amino-3-oxo-4- (phenyl and halophenyl) -2,3-dihydrofurans and specifically describes 5-amino-3-oxo-4 - (phenyl and 4-chlorophenyl) -2,3-dihydrofurans. Japanese Patent No. [deg.] 19090 (Chemical Abstracts 69P10352e) describes certain 2,3-dihydrothiophenes as pharmaceutical agents. Found in Helvetica Chemica Acta, volume 66, pages 362-378
(1983) the mention of 5-N-cyclopropyl-4-phenyl-2methoxycarbonylmethylene-3-furannone in the academic discussion of a chemical synthesis.

   U.S. Patent No. 4,441,910 describes ureidosulfonylfurans and ureidosulfonylthiophenes herbicides.

  
The subject of the present invention is compounds having herbicidal activity both in pre-emergence and in post-emergence and especially good activity

  
pre-emergence against a wide variety of undesirable plants, both broad-leaved and herbaceous. At lower application doses, these compounds also exhibit growth-regulating properties.

  
Plant.

  
The compounds of the invention correspond to the formula:

  

  <EMI ID = 3.1>


  
where R represents a lower alkyl radical of 1 to 4 carbon atoms; cycloalkyl of 3 to 7 carbon atoms; lower alkenyl; haloalkyl of 1 to 4 carbon atoms and of 1 to 3 halogen atoms independently selected from fluorine, chlorine, bromine and iodine atoms; haloalkenyl of 2 to 4 carbon atoms and of 1 to 3 halogen atoms independently selected from fluorine, chlorine, bromine and iodine atoms; lower alkoxy; lower alkylthio; lower alkoxyalkyl of which the alkoxy and alkyl parts independently having 1 to 3 carbon atoms; lower alkylthioalkyl, the alkyl parts of which independently have 1 to 3 carbon atoms; phenyl; naphth1-yle; inden -1-yl; 4-fluorophenyl; arylalkylene

  
from 1 to 3 carbon atoms in the alkylene part

  
and the aryl part of which is a phenyl, naphthl-yl or inden-1-yl radical; or a substituted aryl or arylalkylene radical chosen from those of the formulas:

  

  <EMI ID = 4.1>
 

  

  <EMI ID = 5.1>


  
where one, two or three of R, R, R, R, R and R9 are independently selected from the lower alkyl, lower alkoxy, halo, nitro and haloalkyl radicals having 1 to 3 carbon atoms and 1 to

  
3 identical or different halogen atoms, the

  
  <EMI ID = 6.1>

  
a single bond or an alkylene radical of 1 to 3 carbon atoms,

  
  <EMI ID = 7.1>

  
alkyl of 1 to 4 carbon atoms,

  
R <2> represents a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkoxycarbonylalkyl of 1 to 4 carbon atoms in the alkoxy part and from 1 to 4 carbon atoms in the alkyl part, alkoxy-alkyl of which the alkoxy and alkyl parts independently have 1 to 3 carbon atoms or alkylthioalkyl of which the alkyl parts independently have 1 to 3 carbon atoms, or else

  
  <EMI ID = 8.1>

  
they are united form a saturated or unsaturated nitrogen heterocycle of 3 to 6 atoms in the ring, one of which is a nitrogen atom and the others of which are carbon atoms,

  
X represents a hydrogen atom or a lower alkyl, lower alkoxy, halo or trifluoromethyl radical and can occupy any accessible position of the phenyl radical and

  
Y represents a lower alkyl, lower alkoxy, halo, lower halo-alkyl radical of 1 to 4 carbon atoms and of 1 to 3 identical or different halogen atoms, lower halo-alkoxy of 1 to

  
4 carbon atoms and from 1 to 3 identical or different halogen atoms or lower halo-alkylthio of 1 to 4 carbon atoms and from 1 to 3 identical or different halogen atoms,

  
being understood when Y is a halogen atom,

  
  <EMI ID = 9.1>

  
drogenic and it being also understood that when Y is other than a trifluoromethyl radical, X is other than a hydrogen atom, R is a hydrogen atom and R is a hydrogen atom, then R is a methyl radical, ethyl, propyl, 2-halophenyl, 2alkyl (lower) phenyl or 4-fluorophenyl.

  
A subject of the invention is also the compatible salts of the compounds of formula (I), for example the salts obtained by replacement of the hydro-

  
  <EMI ID = 10.1>

  
  <EMI ID = 11.1>

  
cation compatible or obtained by enolation of the 3-oxo radical after replacement of the hydrogen atom of the amino function.

  
The compounds of formula (I) exist under

  
  <EMI ID = 12.1>

  
also take an asymmetric carbon atom and can exist as optical isomers. Certain compounds can also exist in the form of geometric isomers. The above formula aims to represent all the particular isomers as well as their mixtures and these particular isomers as well as their mixtures form the subject of the invention.

  
The Applicant has also discovered that the presence of a 3-trifluoromethyl radical on the 4-phenyl radical of the compounds of the invention increases

  
in general very significantly the herbicidal activity.

  
According to another aspect, the invention has

  
relates to a herbicidal composition which comprises a compatible excipient and in an effective herbicidal amount the compounds of formula (I) or their compatible salts or else their mixtures.

  
The invention further relates to a method for preventing or controlling the growth of unwanted vegetation, according to which the medium is treated

  
growth and / or foliage of this vegetation, in an effective herbicidal amount, using the compound or compounds of formula (I) and / or their compatible salts.

  
According to another aspect, the subject of the invention is a composition for regulating the growth of plants which comprises a compatible excipient and, in an amount which regulates plant growth, the compounds of formula (I), the compatible salts of formula (I) ) or their mixtures which are capable of modifying the normal growth rate of these plants.

  
The subject of the invention is moreover a process for regulating the growth of plants according to which the growth medium and / or the leaves of these plants are treated, in an amount effective for regulating the growth of plants, by means of the compounds. of formula (I) and / or their compatible salts capable of modifying the normal growth rate of these plants.

  
The invention further relates to chemical intermediates and methods for preparing the compounds of formula (I).

  
The invention is described in more detail below.

  
Typical examples of the compounds of formula (I) in accordance with the invention are given in Examples 2, 3 and 6 to 10. As regards substituents, the preferred compounds are those where R represents a lower alkyl radical, aryl or substituted aryl, more preferably methyl, ethyl, propyl, phenyl or substituted phenyl, especially phenyl, monomethylphenyl or monohalophenyl and in particular methyl, ethyl, n-propyl, 2-halophenyl, 2-alkyl

  
  <EMI ID = 13.1>

  
independently have a hydrogen atom or a methyl, ethyl or n-propyl radical and more advantageously one of R and R2 represents a hydrogen atom and the other represents a hydrogen atom

  
or methyl, ethyl or n-propyl radical, but especially a hydrogen atom or methyl or ethyl radical, in particular methyl; X represents a hydrogen atom and / or Y represents a 3-trifluoromethyl or 3-halo and especially 3-trifluoromethyl radical. The compounds most preferably contain a combination of two or more preferred substituents.

  
The compounds of formula (I) where R <1> and R2 each represent a hydrogen atom and R represents an aryl or substituted aryl radical can be advantageously obtained by the process illustrated diagrammatically below:

  

  <EMI ID = 14.1>


  
where X and Y are as defined above and Z 'represents an aryl or substituted aryl radical.

  
The conversion of a compound (A) into a compound (II) can advantageously be carried out by bringing the compound (A) into contact with a halogen, preferably bromine, in a liquid carboxylic acid in the presence of an inert organic solvent .

  
Normally, this process is carried out at a temperature of about 0 to 100 [deg.] C and preferably about
20 to 30 [deg.] C, for about 4 to 36 hours and preferably about 18 to 24 hours, using about 1.0 to 10.0

  
and preferably from 1.0 to 1.1 mole of halogen per mole of compound (A). Suitable liquid carboxylic acids which can be used are, for example, acetic acid, propionic acid, butyric acid, formic acid etc. When the carboxylic acid is used in excess, it can serve as a solvent

  
or liquid thinner for the reaction system. Other organic solvents which can be used are, for example, liquid halogenated alkanes such as methylene chloride, carbon tetrachloride,

  
chloroform or 1,2-dichloroethane, liquid aromatic hydrocarbons such as benzene or toluene; liquid alkyl ethers such as diethyl ether, dimethyl sulfoxide, dimethylformamide etc., in addition to their compatible mixtures.

  
The results obtained are the best when the halogen used is bromine, but chlorine and iodine are also suitable.

  
The starting compounds of formula (A) can be obtained by the process illustrated diagrammatically below:

  

  <EMI ID = 15.1>


  
  <EMI ID = 16.1> (for example phenyl) or arylalkylene (for example benzyl) and Z ', Y and X are as defined above.

  
This process can advantageously be carried out by bringing the compound (B) into contact with the compound (C) and with a strong base, preferably in an inert organic solvent.

  
Normally, this process is carried out at temperatures of about 0 to 100 [deg.] C and preferably of

  
75 to 85 [deg.] C for about 5 to 36 hours and preferably 18 to 24 hours using 1.0 to 10.0 and preferably 1.0 to 1.2 mole of compound (C) per mole of compound (B). Normally, about 1.0 to 10.0 moles of base are used per mole of compound (C).

  
Suitable strong bases which can be used are, for example, alkali metal alcoholates, such as sodium methylate, sodium ethylate or potassium ethylate, sodium hydride, potassium hydride etc. The strong base is preferably a base which does not release water as a by-product in this reaction system.

  
Suitable inert solvents which can be used are, for example, lower alkanols
(for example methanol, ethanol and propanol),

  
tetrahydrofuran, dimethoxyethane, dioxane etc., in addition to their compatible mixtures. Advantageously, the alkali metal alcoholate is prepared in situ by reaction of an alkali metal with an excess of the alkanol which in turn serves as a solvent for the above reaction.

  
The starting compounds of formulas (B) and
(C) are generally known compounds which can be prepared by known methods or their obvious variants (i.e. by substitution of suitable starting compounds). The preparation

  
of compound (B) is described, for example, in Org.

  
Syn. Coll., Volume 1, 107 (1941) and that of the compound
(C) in Org. Syn. Coll., Volume 1, 270 (1941).

  
  <EMI ID = 17.1>

  
each have a hydrogen atom can be prepared by the general process illustrated schematically by the following reaction equation:

  

  <EMI ID = 18.1>


  
  <EMI ID = 19.1>

  
has a lower alkyl, aryl (for example phenyl) or arylalkylene (for example benzyl) radical.

  
This process can be carried out with advantage by bringing the compound (B) into contact with the compound (E) and a strong base (for example sodium methylate or sodium ethylate), preferably in an inert organic solvent.

  
Normally, this process is carried out at a temperature of about 0 to 100 [deg.] C, preferably 75

  
at 85 [deg.] C in about 5 to 36 hours, preferably 18 to

  
24 hours using about 1.0 to 10.0 and preferably 1.0 to 1.2 moles of compound (E) per mole of compound (B). Suitable inert organic solvents which can be used are, for example, lower alkanols (for example methanol, ethanol, propanol etc.); tetrahydrofuran; dimethoxyethane; ledioxane etc., in addition to their compatible mixtures.

  
Suitable bases which can be used in this process are in particular those indicated above with regard to the reaction of compound (B)

  
with compound (C).

  
The hydroxyesters of formula (E) are generally known compounds which can be obtained by known methods or their obvious variants (for example by means of suitably substituted starting compounds).

  
The compounds of formula I where R and R each represent a hydrogen atom and R represents an alkyl, cycloalkyl, alkoxy, alkoxy-alkyl, alkyl-alkyl, arylalkylene, substituted arylalkylene or alkenylalkyl radical (for example -CH2CH = CH) also be advantageously prepared by the process illustrated schematically below.

  

  <EMI ID = 20.1>


  
  <EMI ID = 21.1>

  
alkoxyalkyl, alkoxy, alkylthioalkyl, arylalkylene, substituted arylalkylene or alkenyl and R represents a lower alkyl radical, preferably methyl.

  
This process can be advantageously carried out by bringing the compound (A ') into contact with a cyclizing agent under suitable reaction conditions, preferably in an inert organic solvent.

  
Normally this process is carried out at a temperature of about 0 to 200 [deg.] C and preferably about 115 to 120 [deg.] C in about 10 to 120 minutes and preferably about 10 to 30 minutes using about 1 to 10 and preferably 1 to 2 moles of cyclization agent per mole of compound (A '). Suitable cyclizing agents which can be used are, for example, anhydrous strong acids, such as sulfuric acid, hydrogen chloride, hydrogen bromide, trifluoroacetic acid, methane sulfonic acid etc. The best results are normally obtained using anhydrous sulfuric acid.

  
Suitable inert organic solvents which can be used are, for example, acetic acid, propionic acid, butyric acid, toluene, xylene etc., in addition to their compatible mixtures.

  
The starting compounds of formula (A ′) can be prepared by the process illustrated diagrammatically below:

  

  <EMI ID = 22.1>


  
  <EMI ID = 23.1>

  
X 'represents a chloro, bromo or iodo radical and

  
M and M 'independently represent a sodium or lithium atom.

  
Although this process is illustrated as having three stages, these are normally

  
and advantageously carried out in situ. Similarly, as usual for such reactions, the operations are preferably carried out in a substantially anhydrous medium under inert gas (for example nitrogen).

  
In the first stage of this process, the compound
(B ') is brought into contact with a non-nucleophilic base, preferably in an inert organic solvent. This stage is normally carried out at a temperature of about 0 to 25 [deg.] C in about 30 minutes to 3 hours using about 1 to 2 and preferably 1 to 1.3 molar equivalents of non-nucleophilic base per mole of compound (B '). Suitable non-nucleophilic bases which can be used are, for example, alkali metal hydrides, such as sodium hydride, potassium hydride etc. and alkali metal amides, such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium diethylamide, lithium diisopropylamide, sodium dimethylamide etc. .

   Sodium hydride is generally preferred because it works very well and is easy to acquire on the market. The alkali metal amides and obviously also the alkali metal hydrides are generally known compounds which can be prepared according to known methods or their obvious variants. For example, the alkali metal amides can be obtained 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 etc, in addition to their compatible mixtures.

  
The second stage can be performed by placing

  
  <EMI ID = 24.1> preferably in an inert organic solvent. As indicated above, this stage of the process is preferably carried out in situ on the reaction product obtained

  
at the first stage. Normally, the second stage is carried out at a temperature of about -78 to 0 [deg.] C in about 1 to 4 hours using about 1 to 2 and preferably 1 to 1.3 molar equivalents of alkylated base.

  
per mole of compound (B ''). Suitable alkyl bases which can be used are, for example, alkyl alkali metals, Grignard alkyl reagents etc. N-butyl lithium is preferably used because it gives good results and is easy to obtain on the market. Appropriate solvents which can

  
to be used are including those listed above

  
about the first stage and other analogs.

  
The third stage can be carried out by bringing the compound (B '' ') into contact with the halide

  
  <EMI ID = 25.1>

  
preferably in an inert organic solvent. The third stage is normally carried out also in situ on the reaction product of the second stage.

  
The third stage of the process is normally carried out at a temperature of -30 to +30 [deg.] C and preferably 22 to 25 [deg.] C in about 1 to 18 hours and

  
preferably 1 to 5 hours using 1 to 10 moles

  
  <EMI ID = 26.1>

  
are especially those indicated above in connection with the first stage of the process and other analogues. The

  
  <EMI ID = 27.1>

  
which can be prepared according to known methods or their obvious variants (for example substitution of suitable reagents and solvents).

  
The starting compounds of formula (B ') can be prepared by the process illustrated schematically below:

  

  <EMI ID = 28.1>


  
where R represents a lower alkyl radical (preferably methyl) and R, Y and X are as defined above.

  
This process can advantageously be carried out by bringing the compound (B) into contact with the compound
(C ') and a strong base under suitable reaction conditions, preferably in an inert organic solvent.

  
This process is normally carried out under the same conditions as those indicated above

  
about the preparation of compound (A), except that

  
Compound C 'replaces Compound C. Compounds

  
They are simple alkyl alkoxy acetates such as

  
methyl methoxyacetate. The preparation of such compounds is conventional.

  
A compound of formula (I) in which R and / or R2 are substituted can be prepared by alkylation of the amino radical of a corresponding compound

  
of formula I '':

  

  <EMI ID = 29.1>


  
  <EMI ID = 30.1> R <2> 'is as defined for R2 except for the hy-

  
  <EMI ID = 31.1>

  
prayed if dialkoylation is desired.

  
This process can be performed by setting

  
  <EMI ID = 32.1>

  
suitable suitable for alkylating primary or secondary amino radicals.

  
For example, the operation can be performed

  
  <EMI ID = 33.1>

  
an inert organic solvent and preferably in the presence of a base. Normally, this process is carried out at temperatures of about 0 to 100 [deg.] C and preferably of

  
20 to 45 [deg.] C in about 1.0 to 72.0 hours and preferably in 2.0 to 18.0 hours. When monoalkylation is desired, about 1.0 to 1.1 mo is normally used

  
  <EMI ID = 34.1>

  
alkylate two hydrogen atoms of amino function, normally used about 1.9 to 4.0 moles of compound

  
  <EMI ID = 35.1>

  
posed in which R <2> 'represents an alkoxy-alkyl or alkylthio-alkyl radical, it is preferred to take a large

  
  <EMI ID = 36.1>

  
mono-alkylation, for example 3 to 6 moles of R <2> 'Z' 'per mole of I' '. Further alkylation can be carried out at a second stage if desired. A modification of R <1> and R2 can also be carried out by first alkylating only one of the two hydrogen atoms of the amino function, then by alkylating the second hydrogen atom of the amino function using an agent alkylation comprising a radical R <2> 'different-

  
  <EMI ID = 37.1>

  
with the nitrogen atom of the amino function a saturated heterocycle can be obtained by means of an agent <EMI ID = 38.1>

  
has Cl or Br. The unsaturated heterocycle R R N can be obtained by means of the appropriate cis-alkenyl dihalide carrying a halogen atom on each of the terminal carbon atoms of the alkenyl radical. Suitable inert organic solvents which can

  
to be used are, for example, liquid halogenated alkanes such as methylene chloride, carbon tetrachloride or dichloroethane, but tetrahydrofuran and similar solvents are also suitable. Suitable bases as acceptors which can be used are, for example, those described above

  
about the reaction of compound (B) with compound

(VS).

  
  <EMI ID = 39.1>

  
feel a lower alkyl radical (for example methyl) and R2 represents a hydrogen atom or lower alkyl radical are advantageously obtained by means of a dialkyl sulfate as alkylating agent. The reaction can be carried out by contacting the compound of formula I in which R <1> and / or R2 represent a hydrogen atom with the desired lower alkyl sulphate in the presence of a strong base and preferably in an inert organic solvent and in the presence also of a phase transfer agent. Normally, the process is carried out at temperatures of about 0 to
100 [deg.] C and preferably from 20 to 45 [deg.] C using 1.0

  
4.0 moles of dialkyl sulfate per mole of compound I. The base is used in excess, normally

  
in an amount of about 2.5 moles. Preferably, the process is carried out in an inert organic solvent

  
such as methylene chloride, carbon tetrachloride, dichloroethane, tetrahydrofuran etc.

  
Suitable strong bases which can be used are, for example, sodium hydroxide, potassium hydroxide, sodium ethylate, sodium carbonate, potassium carbonate etc. Suitable phase transfer agents are agents which transfer hydrophilic ions into a lipophilic organic medium and examples of which are benzyltriethylammonium chloride, chloride

  
tetra-n-butylammonium, methyltrioctylammonium chloride etc.

  
The compatible salts of formula (I) can be prepared according to conventional methods, for example by reaction of a compound of formula (I) in

  
  <EMI ID = 40.1>

  
with a suitable strong base, such as n-butyllithium, sodium hydride, potassium hydride etc. providing the desired cation using the usual techniques

  
  <EMI ID = 41.1>

  
correspondents. The enolic salts can be prepared by reacting the cationic salts of R and / or R with a base according to the usual techniques. Other modifications of the salt cation can also be carried out by ion exchange with an ion exchange resin providing the desired cation.

  
In the methods described above, it

  
it is generally preferable to separate the respective products before carrying out the next stage in the succession of reactions, except when it is a stage described as being carried out in situ or unless expressly indicated otherwise. These products can

  
be isolated from their respective reaction mixtures by any suitable separation and purification technique, such as recrystallization and chromatography. Appropriate separation and purification techniques are illustrated in the examples below.

  
In general, the above reactions are carried out in the liquid phase and the pressure is therefore generally unimportant unless it influences the temperature (boiling point) when the reactions are carried out at reflux. These reactions are therefore generally carried out under pressures of around 300

  
at 3000 mm Hg (0.4 to 4 bars) and advantageously roughly under atmospheric pressure.

  
It should also be noted that when typical or preferred operating conditions are indicated (for example temperature or reaction time, molar ratios of the reactants, amount of solvents, etc.) other operating conditions may also be suitable. The optimal reaction conditions (for example temperature and reaction time, molar ratios, solvents, etc.) may depend on the nature of the reagents and organic solvents, but may be determined according to current optimization techniques.

  
When mixtures of optical isomers are formed, the distinct isomers can be obtained according to the usual splitting techniques. The geometric isomers can be separated according to the usual fractionation techniques which depend on the differences in physical properties between these geometric isomers.

  
For the purposes of the invention, the following terms have the meanings specified below, unless expressly indicated otherwise.

  
By "lower alkyl radicals" is meant straight or branched chain alkyl radicals of 1

  
with 4 carbon atoms in total of primary, secondary or tertiary structure. Typical lower alkyl radicals are methyl, ethyl, npropyl, isopropyl, n-butyl and t-butyl radicals.

  
By "alkylene radicals" is meant straight or branched chain alkylene radicals such as

  

  <EMI ID = 42.1>


  
By "lower alkenyl radicals" is meant alkenyl radicals of 2 to 6 and preferably of 2 to 4 carbon atoms, for example vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2methylprop-1 -enyl etc.

  
By "lower alkoxy radicals" is meant radicals -OR 'where R' represents a lower alkyl radical.

  
By "lower alkyl radicals" is meant radicals -SR 'where R' represents a lower alkyl radical.

  
By "lower alkoxyalkyl radicals",

  
  <EMI ID = 43.1>

  
independently of straight or branched chain alkyl radicals of 1 to 3 carbon atoms.

  
By "lower alkylthioalcoyl radicals",

  
  <EMI ID = 44.1>

  
independently of straight or branched chain alkyl radicals of 1 to 3 carbon atoms.

  
By "lower alkoxycarbonylalkyl radicals" is meant a radical R'OC (O) R "where R 'represents

  
  <EMI ID = 45.1>

  
dical alkylene of 1 to 4 carbon atoms in a straight or branched chain. Alkoxycarbonylalkyl radicals

  
  <EMI ID = 46.1>
-CH (CH3) C (O) OC2H5, etc.

  
By "halo radical" is meant a fluoro, chloro, bromo or iodo radical.

  
By "lower haloalkyl radicals" means haloalkyl radicals of 1 to 4 carbon atoms and from 1 to 3 halogen atoms independently chosen from fluorine, chlorine, bromine and iodine atoms. Preferably the lower haloalkyl radical has 1 or 2 carbon atoms.

  
By "lower haloalkoxy radicals" is meant lower alkoxy radicals bearing 1 to 3 halogen atoms independently chosen from fluorine, chlorine, bromine and iodine atoms.

  
By "aryl radicals" is meant aryl radicals of 6 to 10 carbon atoms such as phenyl, naphthyl and indenyl. Normally, the aryl radical is a phenyl or naphthyl radical because the compounds comprising these radicals are easier to acquire on the market than those comprising other aryl radicals.

  
By "substituted aryl radicals" is meant aryl radicals bearing 1 to 3 substituents independently chosen from lower alkyl, lower alkoxy, halo, nitro and haloalkyl radicals of 1 to 3 carbon atoms and 1 to 3 halogen atoms. Typical substituted aryl radicals are, for example, 2-fluorophenyl, 2-chlorophenyl, 2,6-dimethylphenyl, 4-fluorophenyl, 2-methylphenyl, 2-chloro-3-chloromethylphenyl, 2-nitro-5-methylphenyl, 2, 6-dichlorophenyl, 3-trifluoromethylphenyl, 2-methoxyphenyl, 2-bromonapht-1-yle, 3-methoxyinden1-yl, etc.

  
By "arylalkylene radicals" is meant

  
  <EMI ID = 47.1>

  
and R <3> represents an alkylene radical of 1 to 3 carbon atoms in a straight or branched chain, for example methylene, ethyl, 1-methylethyl or propyl.

  
By "arylalkylene radicals substituted on the aryl radical or substituted on the ring" is meant radicals Ar'R <3> - where Ar 'represents a radical

  
  <EMI ID = 48.1> as defined with respect to arylalkylene.

  
By "saturated nitrogen heterocycle" is meant

  
  <EMI ID = 49.1>

  
of formula

  

  <EMI ID = 50.1>


  
where n represents 1, 2 or 3.

  
By "unsaturated nitrogen heterocycle" about

  
  <EMI ID = 51.1>

  
formulas:

  

  <EMI ID = 52.1>


  
By "compatible salts" is meant salts which do not appreciably modify the herbicidal properties of the compounds from which they are derived. Suitable salts are cationic salts such as those of lithium, sodium, potassium, alkaline earth metals, ammonium, quaternary ammonium etc.

  
The compounds of formula (I) manifest

  
pre-emergence and post-emergence herbicide activity

  
and above all a good herbicidal activity in pre-emergence.

  
In general, for post-emergence application, the herbicidal compounds are applied directly to the foliage or other parts of the plants. For

  
pre-emergence applications, the herbicidal compounds are applied to the growth medium or the growth medium envisaged for the plants. The optimal amount of compound or herbicidal composition depends on the species to which the plants belong, the possible degree of growth in the plants, the part of the plants coming into contact and the extent of the contact. The optimal dose also varies with the general situation
(for example, under cover as in greenhouses rather than in the open air) as well as the nature and degree of the desired effect. In general, for pre-emergence and post-emergence control, the compounds of the invention are applied in doses of approximately 0.02 to 60 kg / ha and

  
preferably about 0.02 to 10 kg / ha.

  
Likewise, although in principle the compounds can be applied in the undiluted state, in current practice they are generally applied in the state of composition comprising an effective amount of the compound or compounds and an appropriate excipient. An acceptable or compatible excipient (excipient acceptable in agriculture) is an excipient which has no appreciable adverse influence on the desired biological effect exerted by the active ingredients, except to dilute them. Normally, the composition contains about 0.05 to

  
95% of the compound (s) of formula (I). Concentrates with a high content and intended to be diluted

  
for application can also be prepared. The excipient can be a solid, a liquid or an aerosol. The compositions can be presented in the form of granules, powders, dusting powders,

  
solutions, emulsions, dispersions, aerosols etc.

  
Suitable solid excipients which can be used are, for example, natural clays (such as kaolin, attapulgite, montmorillonite, etc.), talcs, pyrophyllite, diatomaceous earth, synthetic fine silica, aluminosilicates calcium, tricalcium phosphate etc. Likewise, organic substances such as nutshell flour, cotton seed husk, wheat flour, wood flour, bark flour etc. suitable as excipients.

  
Suitable liquid diluents which can be used are, for example, water, organic solvents (such as hydrocarbons such as benzene, toluene, dimethyl sulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha etc. .) And so on. Suitable aerosol excipients which can be used are

  
those in common use, such as halogenated alkanes, etc.

  
The compositions can also contain different promoters and surfactants which increase

  
the speed of transport of the active ingredient in plant tissue such as organic solvents, wetting agents and oils and, in the case of compositions intended for pre-emergence application, agents which slow down the leaching of the compound or otherwise improve its stability in the soil.

  
The composition may also contain adjuvants, stabilizers, conditioning agents, insecticides, fungicides and, if desired, other compatible herbicides.

  
At low doses, the compounds of the invention show a regulating effect on plant growth and can be used to modify the normal growth rate of plants.

  
The compounds of formula (I) can be applied as regulators of plant growth in pure form, but more practically, like herbicides, they are applied together with an excipient. Excipients of the same kinds as those indicated above with respect to the herbicidal compositions are suitable. Depending on the application envisaged, the composition for the regulation of

  
the growth of the plants can contain other compatible active principles or be applied together with them, for example desiccants, defoliants, surfactants, adjuvants, fungicides and insecticides. Normally, the composition for regulating plant growth contains a total of about 0.005 to 90% by weight of the compound or compounds of formula (I) depending on whether the composition is to be applied directly or must be diluted first.

  
The invention is further illustrated by the following examples. Unless otherwise stated, temperatures are given in degrees Celsius and "room temperature" means about 20

  
at 25 [deg.] C. The percentages are given on a weight basis and by "mole" is meant a gram molecule. By "equivalent" is meant an amount of reactant equal in moles to the number of moles of the other reactant in question. The magnetic resonance spectra of the protons possibly specified (RMP or R. MN) are measured at 60 MHz, the signals being explained in the form of singlets (s), wide singlets (si), doublets (d), double doublets (dd) , triplets
(t), double triplets (dt), quadruplets (q) and multiplets (m). If necessary, the examples are repeated for the preparation of an additional amount of starting compound for the following examples.

  
EXAMPLE 1

  
(3-Trifluoromethylphenyl) benzylcarbonylacetonitrile

  
4.91 g of metallic sodium are added to 110 ml of anhydrous ethanol at room temperature and the mixture is stirred well until all the sodium has dissolved. Then added dropwise

  
a mixture of 18.76 g of (3-trifluoromethylphenyl) acetonitrile and 21.73 g of ethyl phenylacetate and the resulting mixture is heated under reflux for about 18 hours. Then pour the mixture into
300 ml of water and it is extracted three times with ethyl ether. The extracted aqueous layer is adjusted to

  
a pH of about 1 with 10% by weight aqueous hydrochloric acid and it is extracted again three times with ethyl ether. The organic layer is washed twice with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and evaporated to dryness in vacuo to give
22.6 g of the title compound.

  
Likewise, using in the above procedure the suitably substituted phenylacetonitrile and the suitably substituted ethyl phenylacetate, the following compounds can be prepared:

  
(5-chloro-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(4-chloro-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(2-bromo-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(6-fluoro-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(4-methyl-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(5-methoxy-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(6-methyl-3-trifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(3,5-ditrifluoromethylphenyl) benzylcarbonylacetonitrile;

  
(3-difluoromethoxyphenyl) benzylcarbonylacetonitrile;
(3-trifluoromethoxyphenyl) benzylcarbonylacetonitrile;
(3-trifluoromethylphenyl) - (4-fluorobenzylcarbonyl) acetonitrile;

  
(3-trifluoromethylphenyl) -1-naphthylmethylene-acetonitrile;

  
(2-chloro-3-methylphenyl) benzylcarbonylacetonitrile;
(4-ethyl-3-methylphenyl) benzylcarbonylacetonitrile;
(5-methoxy-3-chlorophenyl) benzylcarbonylacetonitrile;
(3-iodophenyl) benzylcarbonylacetonitrile;
(3-difluoromethylthiophenyl) benzylcarbonylacetonitrile;
(3-trifluoromethylthiophenyl) benzylcarbonylacetonitrile;
(3,5-diethoxyphenyl) benzylcarbonylacetonitrile;
(3-bromophenyl) - (2-nitrobenzylcarbonyl) acetonitrile;
(2-chloro-3-methylphenyl) benzylcarbonylacetonitrile;
(3-bromo-2-ethylphenyl) naphth - 1-ylmethylenecarbonylacetonitrile;

  
(2,3-dimethylphenyl) -beta-naphth-1-ylmethylcarbonylacetonitrile;

  
(3-chlorophenyl) benzylcarbonylacetonitrile;
(3-methylphenyl) benzylcarbonylacetonitrile;
(3-t-butoxyphenyl) benzylcarbonylacetonitrile;
(3-propylphenyl) benzylcarbonylacetonitrile;
(3-bromophenyl) benzylcarbonylacetonitrile;
(3-iodophenyl) - (3-nitrobenzylcarbonyl) acetonitrile;
(3-trifluoromethylphenyl) - (2,3-dichlorobenzylcarbonyl) acetonitrile;

  
(3-methoxyphenyl) -1-naphthylmethylenecarbonylacetonitrile;

  
(3-trifluoromethyl) - (3-chloro-8-fluoronapht-1-ylmethylenecarbonyl) acetonitrile;

  
(3-trifluoromethyl) - [(2-trifluoromethyl-3-methyl-8-

  
  <EMI ID = 53.1>

  
  <EMI ID = 54.1>

  
acetonitrile, and

  
(3-trifluoromethyl) - (2-fluoroindén-1-ylméthylènecarbonyl) acetonitrile.

  
EXAMPLE 2

  
  <EMI ID = 55.1>

  
dihydrofuran.

  
A solution of
12.65 g of bromine in 20 ml of glacial acetic acid

  
to a solution of 21.8 g of (3-trifluoromethylphenyl) benzylcarbonylacetonitrile in 60 ml of acetic acid. The reaction mixture is stirred for about 16 hours at room temperature. The reaction mixture is poured into 250 ml of water and the resulting mixture is extracted three times with ethyl ether. The organic extracts are washed with saturated aqueous sodium bicarbonate, dried over magnesium sulphate and concentrated in vacuo to give 8.4 g of a white solid giving 7.0 g of the title compound by drying .

  
Likewise, using the compounds of Example 1 in the above procedure, 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-dihydrofuran;

  
2-phenyl-3-oxo-4- (2-bromo-3-trifluoromethylphenyl) -5amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (6-fluoro-3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (4-methyl-3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (5-methoxy-3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (6-methyl-3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3,5-ditrifluoromethylphenyl) -5-amino2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-difluoromethoxyphenyl) -5-amino-2,3dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethoxyphenyl) -5-amino2,3-dihydrofuran;

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

  
2- (1-naphthyl) -3-oxo-4- (3-trifluoromethylphenyl) -5amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (2-chloro-3-methylphenyl) -5-amino2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (4-ethyl-3-methylphenyl) -5-amino2, 3-dihydrofuran;

  
2-phenyl-3-oxo-4- (5-methoxy-3-chlorophenyl) -5-amino2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-iodophenyl) -5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-difluoromethylthiophenyl) -5-amino2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-amino2, 3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3,5-diethoxyphenyl) -5-amino-2,3-dihydrofuran;

  
2- (2-nitrophenyl) -3-oxo-4- (3-bromophenyl) -5-amino-2,3dihydrofuran;

  
2-phenyl-3-oxo-4- (2-chloro-3-methylphenyl) -5-amino2,3-dihydrofuran;

  
2- (1-naphthyl) -3-oxo-4- (3-bromo-2-ethylphenyl) 5-amino2,3-dihydrofuran;

  
2- (1-naphthyl) -3-oxo-4- (2,3-dimethylphenyl) -5-amino-2,3dihydrofuran;

  
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-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-propylphenyl) -5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-bromophenyl) -5-amino-2,3-dihydrofuran;

  
2- (3-nitrophenyl) -3-oxo-4- (3-iodophenyl) -5-amino-2,3dihydrof uranne;

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

  
2- (1-naphthyl) -3-oxo-4- (3-methoxyphenyl) -5-amino-2,3dihydrofuran;

  
2- (3-chloro-8-fluoronapht-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (2-trifluoromethyl-3-methyl-8-methoxy-naphth-1-yl) 3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran;

  
2-inden-1-yl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino2,3-dihydrofuran, and

  
2- (2-fluoroindén-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran.

  
EXAMPLE 3

  
2-Methyl-3-oxo-4- (3-trifluoromethylphenyl) 5-amino-
2.3-dihydrofuran

  
100 ml of ethanol are introduced into a 500 ml dry round bottom flask with three necks fitted with a mechanical stirrer, an inlet bulb and a reflux condenser. 3.5 g of sodium are added to the stirred solvent. After all the metal has dissolved,

  
to the reaction mixture is added dropwise a solution of 13.0 g of ethyl L - (+) - lactate and
18.5 g of m-trifluoromethylphenylacetonitrile in 30 ml of ethanol. The mixture turns dark red and

  
at the end of the addition, it is heated to reflux overnight (about 18 hours). The mixture is then cooled to room temperature and poured into 300 ml of water, then the resulting mixture is acidified (pH about 1) with 10% hydrochloric acid. The mixture is then extracted with ether
(three times) and the organic extracts are washed (twice) with saturated aqueous sodium bicarbonate,

  
dried over magnesium sulfate and concentrated in vacuo to obtain a thick oil.

  
The oil is taken up in an ether / petroleum ether mixture to obtain a yellow powder.

  
the desired crystallized compound. Two crops of crystals are collected to obtain a total of 4.7 g of the title compound.

  
Likewise, using the starting compounds suitably substituted in the above procedure, the following compounds can be prepared:
2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3dihydrofuran;

  
2-ethyl-3-oxo-4- (5-chloro-3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

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

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

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

  
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-dihydrofuran;

  
2-methyl-3-oxo-4- (3-difluoromethoxyphenyl) -5-amino2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3-trifluoromethoxyphenyl) -5-amino2,3-dihydrofuran;

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

  
2- (2-chlorovinyl) -3-oxo-4- (5-propoxy-3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (2-methoxy-3-chlorophenyl) -5-amino2,3-dihydrofuran;

  
2-ethyl-3-oxo-4- (2-chloro-3-fluorophenyl) -5-amino-2,3dihydrofuran;

  
2-vinyl-3-oxo-4- (3-methyl-4-methoxyphenyl) -5-amino2,3-dihydrofuran;

  
2-allyl-3-oxo-4- (3,6-dimethylphenyl) -5-amino-2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (3-trifluoromethyl-4-bromophenyl) -5-amino-2,3-dihydrofuran;

  
2- (2-chlorovinyl) -3-oxo-4- (3-nitro-4-methylphenyl) -5amino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3-methoxyphenyl) -5-amino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3-difluoromethylthiophenyl) -5-amino2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-amino2,3-dihydrofuran;

  
2-ethyl-3-oxo-4- (3-chlorophenyl) -5-amino-2,3-dihydrofuran;

  
2-vinyl-3-oxo-4- (3-methylphenyl) -5-amino-2,3-dihydrofuran;

  
  <EMI ID = 56.1>

  
2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (4-fluorophenyl) -5-amino-2,3dihydrofuran;

  
2- (2-chlorovinyl) -3-oxo-4- (2-bromophenyl) -3-oxo-5-amino2,3-dihydrofuran;

  
2-propyl-3-oxo-4- (2-methoxy-3-chlorophenyl) -5-amino-2,3-dihydrofuran;

  
2-butyl-3-oxo-4- (2-chloro-3-fluorophenyl) -5-amino-2,3dihydrofuran;

  
2-vinyl-3-oxo-4- (3-chloro-4-methoxyphenyl) -5-amino-2,3dihydrofuran;

  
2-allyl-3-oxo-4- (3,5-dimethylphenyl) -5-amino-2,3-dihydrofuran;

  
2- (trifluoromethyl) -3-oxo-4- (3-trifluoromethyl-5bromophenyl) -5-amino-2,3-dihydrofuran; 2- (2-chlorovinyl) -3-oxo-4- (3-fluoro-4-methylphenyl) -

  
  <EMI ID = 57.1>

  
2-phenyl-3-oxo-4- (3-methoxyphenyl) -5-amino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3,5-difluorophenyl) -5-amino-2,3-dihydrofuran;

  
2-vinyl-3-oxo-4- (3,5-diethylphenyl) -5-amino-2,3-dihydrofuran;

  
2-allyl-3-oxo-4- (3-propoxyphenyl) -5-amino-2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (3-fluorophenyl) -5-amino2,3-dihydrofuran;

  
2-propyl-3-oxo-4- (3-bromophenyl) -5-amino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (2-iodo-3-fluorophenyl) -5-amino-2,3dihydrofuran;

  
2-benzyl-3-oxo-4- (2-isopropoxy-3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

  
2- (3-chlorophenyl) -3-oxo-4- (2,3-dimethylphenyl) -5-amino2,3-dihydrofuran;

  
2-naphth-1-yl-3-oxo-4- (3-trifluoromethyl-4-bromophenyl) 5-amino-2,3-dihydrofuran;

  
2- (3-methylphenyl) -3-oxo-4- (3-butyl-4-methylphenyl) -3oxo-5-amino-2,3-dihydrofuran;

  
2- (3-fluorophenyl) -3-oxo-4- (3-chlorophenyl) -5-amino2,3-dihydrofuran;

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

  
2- (3-methylnaphth-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran;

  
2- (2'-chlorovinyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

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

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

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

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

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

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

  
2- (1-propylthioethyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran.

  
EXAMPLE 4

  
(3-Trifluoromethylphenyl) methoxyacetylacetonitrile

  
5.6 g of metallic sodium are added to

  
120 ml anhydrous ethanol at room temperature

  
under a nitrogen atmosphere, which releases hydrogen. When the hydrogen is released,

  
a mixture of 30 g of (3-trifluoromethylphenyl) acetonitrile and 18.5 g of methoxyacetate is added

  
methyl in anhydrous ethanol and heated

  
the resulting mixture at reflux for 3 to 4 hours.

  
The mixture is then poured into 300 ml of water and the new mixture is extracted three times with petroleum ether. The remaining aqueous phase is acidified with

  
10% aqueous hydrochloric acid to a pH of about 1 and extracted three times with ethyl ether. The extracts are mixed in ethyl ether, washed twice with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and concentrated by evaporation. The concentrate is evaporated under high vacuum to obtain an oil which is triturated in ethyl ether. The mixture is then filtered to separate the solids

  
and the filtrate is evaporated under vacuum to collect
36.9 g of the title compound, which is a brown solid.

  
Likewise by means of other mono or disubstituted phenylacetonitriles on the phenyl radical instead of (3-trifluoromethylphenyl) acetonitrile, the above procedure gives the monosubstituted and disubstituted derivatives on the phenyl radical analogous to the compound announced in the title.

  
EXAMPLE 5

  
(3-Trifluoromethylphenyl) -2-methoxyisovalerylacetonitrile

  
10 g of (3-trifuoromethylphenyl) methoxyacetylacetonitrile are added dropwise to a dispersion of 1.87 g of sodium hydride in 20 ml of tetrahydrofuran at approximately 0 [deg.] C in a nitrogen atmosphere, which gives release hydrogen. When no evolution of hydrogen is observed, the mixture is cooled to about -78 [deg.] C and 24.3 ml of 1.6M n-butyllithium in hexane is added dropwise. . The mixture is stirred for 90 minutes at
-78 [deg.] C, then stirred for 20 minutes at about 0-4 [deg.] C. Then added dropwise 3.9 ml
(approximately 6.64 g) of 2-iodopropane and the mixture is stirred overnight (approximately 14-16 hours). The mixture is then poured into water, the new mixture is acidified with 10% aqueous hydrochloric acid and extracted three times with ethyl ether.

   We combine the extracts, we dry them

  
over magnesium sulfate and concentrated in vacuo to obtain 11.4 g of the title compound which is an oil.

  
Likewise, by replacing iodopropane in

  
the above procedure with the iodinated, brominated or chlorinated derivative comprising an alkyl, aryl or

  
suitable substituted aryl, the following compounds can be obtained:

  
(3-trifluoromethylphenyl) - (2-methoxy-3-phenylpropionyl) acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (2-fluorophenyl) propionyl] acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (3-methylphenyl) propionyl] acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (2-ethoxyphenyl) propionyl] acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (3-nitrophenyl) propionyl] acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (2-trifluoromethylphenyl) propionyl] acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (2-chloro-3propylphenyl) propionyl] acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (2-nitro-3methoxyphenyl) propionyl] acetonitrile;
(3-trifluoromethylphenyl) - [2-methoxy-3- (2-fluoro-3-2 ',

  
  <EMI ID = 58.1>

  
(3-trifluoromethylphenyl) - [2-methoxy-3- (2,3-dichloro6-methylphenyl) propionyl] acetonitrile;
(3-trifluoromethylphenyl) - (2-methoxy-4-phenylbutyryl) acetonitrile;

  
(3-trifluoromethylphenyl) - [2-methoxy-5- (2-bromophenyl) valeryl] acetonitrile;

  
(3-trifluoromethylphenyl) - (2-methoxy-3-methyl-4-phenylbutyryl) acetonitrile;

  
(3-trifluoromethyl) - (2-methoxy-3-naphth-1-ylpropionyl) acetonitrile;

  
(3-trifluoromethyl) - [2-methoxy-3- (2-fluoronapht-1-yl) propionyl] acetonitrile;

  
  <EMI ID = 59.1>

  
propionyl] acetonitrile;

  
(3-trifluoromethyl) - [2-methoxy-3- (6-nitronapht-1-yl) propionyl] acetonitrile;

  
(3-trifluoromethyl) - [2-methoxy-3- (7-trifluoromethyl-

  
  <EMI ID = 60.1>

  
(3-trifluoromethyl) - (2-methoxy-4-naphth-1-ylbutyryl) acetonitrile;

  
(3-trifluoromethyl) - [2-methoxy-5- (8-fluoronapht-1-yl) valeryl] acetonitrile;

  
  <EMI ID = 61.1>

  
l-yl) propionyl] acetonitrile.

  
Similarly, using other phenylmethoxyacetylacetonitriles mono or disubstituted on the phenyl radical instead of (3-trifluoromethylphenyl) - (2-

  
  <EMI ID = 62.1>

  
above the mono- and disubstituted derivatives on the phenyl radical corresponding to the above compounds.

  
EXAMPLE 6

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

  
The mixture is heated at reflux for 30 minutes, then concentrated by evaporation under vacuum, a mixture of 11.4 g of (3-trifluoromethylphenyl) - (2-methoxyisovaleryl) acetonitrile and 7.8 g of concentrated sulfuric acid in 50 ml acetic acid. The concentrate is mixed with diethyl ether,

  
the mixture is washed three times with hydroxide

  
  <EMI ID = 63.1>

  
magnesium and concentrated by evaporation to

  
get an oil. We grind the oil in a mixture
80:20 by volume of ethyl acetate and petroleum ether and allowed to stand overnight

  
(2 to 4 p.m.). The

  
solids which are washed three times with a mixture 80:20

  
by volume of ethyl acetate and petroleum ether

  
to obtain 2.9 g of the desired compound.

  
Likewise, using 3-trifluoromethylphenyldimethoxy-acetylacetonitrile, which can be obtained according to the process

  
of Example 1, and the other compounds mentioned in Example 5,

  
the following compounds can be obtained by the above procedure:
2-methoxy-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3dihydrofuran;

  
2-benzyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino2,3-dihydrofuran,

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

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

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

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

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

  
2- (2-trifluoromethylbenzyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (2-chloro-3-propylphenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (2-nitro-3-methoxyphenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (2-fluoro-3-2 ', 2'-dichloroethylbenzyl) -3-oxo-4-
(3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (2,3-dichloro-6-methylbenzyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (beta-phenethyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-amino-2,3-dihydrofuran;

  
2- [3- (2-bromophenyl) propyl] -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran;

  
  <EMI ID = 64.1>

  
methylphenyl) -5-amino-2,3-dihydrofuran; 2-naphth-1-ylmethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran;

  
2- (2-fluoronaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (3-butylnaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (5-methoxynapht-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (6-nitronapht-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (7-trifluoromethylnaphth-1-ylmethylene) -3-oxo-4- (3trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (2-chloro-8-methylnaphth-1-ylmethylene) -3-oxo-4- (3trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl) -3-oxo4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran; 2- (beta-naphth-1-ylethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran;

  
2- [beta- (8-fluoronaphth-1-yl) ethyl] -3-oxo-4- (3-trifluo-romethylphenyl) -5-amino-2,3-dihydrofuran;

  
  <EMI ID = 65.1>

  
methylphenyl) -5-amino-2,3-dihydrofuran; 2-inden-1-ylmethylene-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran and

  
2- (2-fluoroinden-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3-dihydrofuran.

  
Likewise, using in the above procedure the monosubstituted and disubstituted analog derivatives of the starting compound for the above compounds, the radical analogs 4- (3-methylphenyl), 4- (3-beta) can be obtained -fluoroethoxyphenyl), 4- (3-difluoromethylenethiophenyl), 4- (3-chlorophenyl), 4- (2-bromo-3-trifluoromethylphenyl) and 4- (methyl-3difluoromethylenethiophenyl) of the above compounds. EXAMPLE 7 -

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

  
About 1 g of solid sodium hydroxide in 4.0 ml of water is added to a mixture of 3 g of 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino-2,3- dihydrofuran in 50 ml of methylene chloride at room temperature, then 1.19 g of dimethyl sulfate and 0.21 g of benzyltriethylammonium chloride are added. The resulting two-phase mixture is stirred

  
at room temperature for about 2 hours, then washed three times with water, dried over

  
magnesium sulfate and concentrated by evaporation in vacuo. The residues are purified by chromatography on silica gel which is eluted with a mixture of tetrahydrofuran and chloroform to obtain

  
the compound announced in the title.

  
Likewise, using in the above procedure the products of Examples 2, 3 and 6 as starting compounds, the corresponding 5-methylamine homologous compounds 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-dihydrofuran;

  
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-ditrifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-difluoromethoxyphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethoxyphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5-methylamino-2,3-dihydrofuran,

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

  
  <EMI ID = 66.1>

  
methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (2-chloro-3-methylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (4-ethyl-3-methylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (5-methoxy-3-chlorophenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-iodophenyl) -5-methylamino-2,3-di-hydrofuran;

  
  <EMI ID = 67.1>

  
2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3,5-diethoxyphenyl) -5-methylamino2,3-dihydrofuran;

  
2- (2-nitrophenyl) -3-oxo-4- (3-bromophenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (2-chloro-3-methylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2- (1-naphthyl) -3-oxo-4- (3-bromo-2-ethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2- (1-naphthyl) -3-oxo-4- (2,3-dimethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-chlorophenyl) -5-methylamino-2,3dihydrofuran;

  
2-phenyl-3-oxo-4- (3-methylphenyl) -5-methylamino-2,3dihydrofuran;

  
2-phenyl-3-oxo-4- (3-butoxyphenyl) -5-methylamino-2,3dihydrofuran;

  
2-phenyl-3-oxo-4- (2-propylphenyl) -5-methylamino-2,3dihydrofuran;

  
  <EMI ID = 68.1>

  
hydrofuran;

  
2- (3-nitrophenyl) -3-oxo-4- (3-iodophenyl) -5-methylamino2,3-dihydrofuran;

  
2- (2,3-dichlorobenzyl) -3-oxo-4- (2-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2- (1-naphthyl) -3-oxo-4- (3-methoxyphenyl) -5-methylamino2,3-dihydrofuran;

  
2- (3-chloro-8-fluoronapht-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-trifluoromethyl-3-methyl-8-methoxynapht-1-yl) -3oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-di-hydrofuran;

  
2-inden-1-yl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2- (2-fluoroindén-1-yl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-ethyl-3-oxo-4- (5-chloro-3-trifluoromethylphenyl) -5methylamino-2,3-dihydrofuran;

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

  
2-vinyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-allyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino2,3-dihydrofuran;

  
2-allyl-3-oxo-4- (2-methoxy-3-trifluoromethylphenyl) -5methylamino-2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (3-trifluoromethylphenyl) -5methylamino-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) -5methylamino-2,3-dihydrofuran;

  
2- (2-chlorovinyl) -3-oxo-4- (5-nitro-3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (2-methoxy-3-chlorophenyl) -5-methylamino-2,3-dihydrofuran;

  
2-ethyl-3-oxo-4- (2-chloro-3-fluorophenyl) -5-methylamino2,3-dihydrofuran;

  
2-vinyl-3-oxo-4- (3-methyl-4-methoxyphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-allyl-3-oxo-4- (3,6-dimethylphenyl) -5-methylamino2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (3-trifluoromethyl-4-bromophenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-chlorovinyl) -3-oxo-4- (3-nitro-4-methylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3-methoxyphenyl) -5-methylamino-2,3dihydrofuran;

  
2-methyl-3-oxo-4- (3-difluoromethylthiophenyl) -5-methylamino-2,3-dihydrofuran

  
2-methyl-3-oxo-4- (3-trifluoromethylthiophenyl) -5methylamino-2,3-dihydrofuran;

  
2-ethyl-3-oxo-4- (3-chlorophenyl) -5-methylamino-2,3dihydrofuran;

  
2-vinyl-3-oxo-4- (3-methylphenyl) -5-methylamino-2,3dihydrofuran;

  
  <EMI ID = 69.1>

  
methylamino-2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (4-fluorophenyl) -5-methylamino-2,3-dihydrofuran;

  
2- (2-chlorovinyl) -3-oxo-4- (2-bromophenyl) -5-methylamino2,3-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-methylamino2,3-dihydrofuran;

  
2-trifluoromethyl-3-oxo-4- (3-trifluoromethyl-5-bromophenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-chlorovinyl) -3-oxo-4- (3-fluoro-4-methylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-methoxyphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3,5-difluorophenyl) -5-methylamino2,3-dihydrofuran;

  
2-vinyl-3-oxo-4- (3,5-diethylphenyl) -5-methylamino2,3-dihydrofuran;

  
2-allyl-3-oxo-4- (3-propoxyphenyl) -5-methylamino-2,3dihydrofuran,

  
2-trifluoromethyl-3-oxo-4- (3-fluorophenyl) -5-methylamino-2,3-dihydrofuran;

  
2-propyl-3-oxo-4- (2-bromophenyl) -5-methylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (2-iodo-3-fluorophenyl) -5-methylamino2,3-dihydrofuran;

  
2-benzyl-3-oxo-4- (2-isopropoxy-3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
  <EMI ID = 70.1>

  
5-methylamino-2,3-dihydrofuran;

  
2- (3-methylphenyl) -3-oxo-4- (3-butyl-4-methylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2- (3-fluorophenyl) -3-oxo-4- (3-chlorophenyl) -5-methylamino-2,3-dihydrofuran;

  
2- (2,3,5-trifluorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran, and 2- (3-methylnaphth-1-yl) -3-oxo -4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (chlorovinyl) -3-oxo-4- (3-trifluoromethylphenyl) -5methylamino-2,3-dihydrofuran;

  
2-fluoromethyl-3-oxo-4- (3-trifluoromethylphenyl) -5methylamino-2,3-dihydrofuran;

  
2-methoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2-propoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2-ethoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2- (2-methoxypropyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2-methylthiomethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran, 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-dihydrofuran;

  
2- (3-methylbenzyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2- (2-ethoxybenzyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2- (3-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-methylamino-2,3-dihydrofuran; 2- (chloro-3-propylphenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-nitro-3-methoxyphenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2-fluoro-3-2 ', 2'-dichloroethylbenzyl) -3-oxo-4- (3trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (2,3-dichloro-6-methylbenzyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (beta-phenethyl) -3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
  <EMI ID = 71.1> phenyl) -5-methylamino-2,3-dihydrofuran; 2-naphth-1-ylmethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran;

  
2- (2-fluoronaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (3-butylnaphth-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
  <EMI ID = 72.1>

  
methylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (6-nitronapht-1-ylmethylene) -3-oxo-4- (3-trifluoro-

  
  <EMI ID = 73.1>

  
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 (3trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- (3-methoxy-5-nitro-7-fluoromethylnaphth-1-yl) -3-oxo4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2-methoxy-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
2- (beta-naphth-1-ylethyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran; 2- [beta- (8-fluoronaphth-1-yl) ethyl] -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran;

  
  <EMI ID = 74.1>

  
2-inden-1-ylmethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methylamino-2,3-dihydrofuran and

  
2- (2-fluoroinden-1-ylmethylene) -3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran.

  
Likewise, by roughly doubling the amount of dimethyl sulfate and increasing the reaction time, the 5-dimethylamine homologs of the above compounds can be prepared. Likewise, by using diethyl sulfate instead of dimethyl sulfate, the corresponding 5-ethylamine and 5-diethylamine homologs of the above compounds can be prepared.

  
EXAMPLE 8 -

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

  
1 g of sodium hydroxide in 4.0 ml of water is added to a mixture of 4.0 g of 2- (2-fluorophenyl) -3-oxo-4- (3-trifluoromethylphenyl) -5-amino- 2,3dihydrofuran in 80 ml of methylene chloride

  
at room temperature, then 1.44 g of allyl bromide and 0.27 g of benzyltriethylammonium chloride are added. The resulting two-phase mixture is stirred at room temperature for about 18 hours after which it is washed three times with water, dried over magnesium sulfate and concentrated in vacuo. The residue is purified by chromatography on silica gel which is eluted with chloroform to collect 2.5 g of the desired tablet.

  
Similarly, by applying this procedure to the products mentioned in Examples 2, 3 and 6, their 5-allylamine analogs can be obtained. Likewise also, by roughly doubling the amount of allyl bromide and sodium hydroxide, their 5-diallylamine analogs can be prepared.

  
Similarly, using ethyl bromide instead of allyl bromide, the corresponding 5-ethylamine and 5-diethylamine analogs can be prepared.

  
Similarly, according to the same procedure, using respectively methoxymethyl bromide, ethylthiomethyl bromide, methyl bromoacetate, methyl 2-bromobutyrate, 1,5-dibromopentane and cis-1,4-dibromobut -1,3-diene instead of an alkyl bromide, the analogs 5-methoxymethylamines, 5-ethylthiomethylamines, can be obtained,

  
  <EMI ID = 75.1>

  
propylamines), 5-piperidin-1-ylés and 5-pyrrol-l-ylés of the products mentioned in examples 2, 3 and 6, for example:

  
2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxymethylamino-2,3-dihydrofuran;

  
2-methyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxymethylamino-2,3-dihydrofuran;

  
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-dihydrofuran;

  
2-ethoxymethylene-3-oxo-4- (3-trifluoromethylphenyl) -5ethylthiomethylamino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-ethylthiomethylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxycarbonylmethylamino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxycarbonylmethylamino-2,3-dihydrofuran; 2-methylthiomethylene-3-oxo-4- (3-trifluoromethylphenyl) 5-methoxycarbonylmethylamino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methoxycarbonylmethylamino-2,3-dihydrofuran;

  
2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-methoxycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-methyl-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-methoxycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-fluoro-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-metho-xycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-ethyl-3-oxo-4- (3-trifluoromethylphenyl) -5- (1-methoxycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-napht-1-yl-3-oxo-4- (3-trifluoromethylphenyl) -5-
(1-methoxycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-inden-1-yl-3-oxo-4- (3-trifluoromethylphenyl) -5-
(1-methoxycarbonylprop-1-yl) amino-2,3-dihydrofuran; 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-piperidin-1-yl-2,3-dihydrofuran, and

  
2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-pyrrol1-yl-2,3-dihydrofuran, etc.

  
Likewise, by applying the above procedures using the 5-methylamine products of Example 7 as starting materials, the analogs 5- (N-methyl-N-allylamines), 5- (N- methylN-ethylamine), 5- (N-methyl-N-methoxymethylamine), 5- (N-methyl-N-ethylthiomethylamine), 5- (N-methyl-Nmethoxycarbonylmethylamine) and 5- (N-methyl-N-l ' -methoxycarbonylpropylamines).

  
EXAMPLE 9

  
Lithium salt of 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-methylamino-2,3-dihydrofuran (R = -CH-,, R <2> = Li)

  
5.4 ml of 1.6M n-butyllithium in hexane are added dropwise to a stirred solution of 2.86 g of 2-phenyl-3-oxo-4- (3-trifluoromethylphenyl) -5-amino- 2,3-dihydrofuran in 25 ml of tetrahydrofuran at -30 [deg.] C. The resulting mixture was stirred for 20 minutes and then concentrated in vacuo to obtain 2.8 g of the title compound which is a light brown solid.

  
Elementary analysis

  
calculated C, 63.74; H, 3.84; N, 4.13%

  
found C, 61.82; H, 4.90; N, 3.48%

  
Likewise, by adapting the above procedure, the corresponding lithium salts of the compounds of Examples 2 to 5 can also be prepared. EXAMPLE 10

  
The compounds of Table A are prepared below using the appropriate starting compounds and according to the suitable procedures described in the examples above.

  

  <EMI ID = 76.1>


  

  <EMI ID = 77.1>
 

  

  <EMI ID = 78.1>


  

  <EMI ID = 79.1>
 

  

  <EMI ID = 80.1>


  

  <EMI ID = 81.1>
 

  

  <EMI ID = 82.1>


  

  <EMI ID = 83.1>
 

  

  <EMI ID = 84.1>


  

  <EMI ID = 85.1>


  

  <EMI ID = 86.1>
 

  

  <EMI ID = 87.1>


  

  <EMI ID = 88.1>
 

  

  <EMI ID = 89.1>


  

  <EMI ID = 90.1>
 

  

  <EMI ID = 91.1>


  

  <EMI ID = 92.1>
 

  
EXAMPLE 11

  
The pre-emergence and post-emergence activity of the compounds of Table A are tested, according to the procedures indicated below, against various herbaceous and broad-leaved plants comprising a cereal crop and a broad-leaved crop. The compounds tested are identified by the number they bear in Table A.

  
Pre-emergence herbicide effect.

  
The pre-emergence herbicidal effect is determined as specified below.

  
Test solutions of the various compounds are prepared by dissolving 355.5 mg of the test compound in 15 ml of acetone. 2 ml of acetone containing 110 mg of a nonionic surfactant are added to the solution. 12 ml of this stock solution are added

  
to 47.7 ml of water containing the same nonionic surfactant in a concentration of 625 mg / liter.

  
Seed of the test vegetation is planted in an earthen pot and the test solution is sprayed uniformly on the surface of the earth in a dose of 27.5 or 15.6 / ug / cm <2>, as shown in Table 1.

  
We irrigate the sheltered pot in a greenhouse. We irrigate the pot intermittently and we observe the emergence of shoots, the health of emerging shoots etc. during 3 weeks. At the end of this period, the herbicidal efficacy is evaluated on the basis of physiological observations. We work on a scale from 0 to 100 where 0 corresponds to the absence of phytotoxicity and 100 corresponds to complete destruction. Results are summarized

  
in table 1.

  
Post-emergence herbicide effect

  
The compound to be tested is presented in the same way as for the pre-emergence test. We spray

  
the solution uniformly on two similar pots containing plants having reached a dimension of

  
5 to 7.5 cm (except for wild oats, soybeans and creeping bentgrass which reached 7.5 to 10 cm), the dose being 27.5, ug / cm and the pots containing 15

  
to 25 plants. After drying the plants, they are kept in the greenhouse and irrigated intermittently through the bottom of the pots as needed. The phytotoxic and physiological effects on plants and the morphological response to treatment are periodically observed. After 3 weeks, the herbicidal efficacy is evaluated on the basis of these observations. We work on a scale from 0 to 100 where 0 corresponds to the absence of phytotoxicity and 100 corresponds to complete destruction. The results are summarized in Table 2.

  

  <EMI ID = 93.1>


  

  <EMI ID = 94.1>
 

  

  <EMI ID = 95.1>


  

  <EMI ID = 96.1>
 

  

  <EMI ID = 97.1>


  

  <EMI ID = 98.1>
 

  

  <EMI ID = 99.1>


  

  <EMI ID = 100.1>
 

  

  <EMI ID = 101.1>


  

  <EMI ID = 102.1>
 

  

  <EMI ID = 103.1>


  

  <EMI ID = 104.1>
 

  

  <EMI ID = 105.1>


  

  <EMI ID = 106.1>
 

  

  <EMI ID = 107.1>


  

  <EMI ID = 108.1>
 

  

  <EMI ID = 109.1>


  

  <EMI ID = 110.1>
 

  

  <EMI ID = 111.1>


  

  <EMI ID = 112.1>
 

  
As can be seen from Table 1, the compounds

  
of the invention generally have excellent broad spectrum pre-emergent phytotoxic activity

  
and this is especially so for compounds n [deg.] 2, 4,

  
7, 9, 12, 14, 16 and 22. In addition, as is clear

  
from Table 2, the compounds generally also have a post-emergence phytotoxic activity against the broadleaf plants and sometimes against certain herbaceous plants, and this is especially the case with the compounds

  
n [deg.] 7, 9, 12, 14, 16, 22 and 23. It can also be observed that the corresponding comparison compounds are much less active than the compounds of the invention.

  
Although various embodiments and details have been described to illustrate the invention, it

  
It goes without saying that it is susceptible to numerous variations and modifications without going beyond its scope.


    

Claims (45)

1 - Compound of formula:  <EMI ID = 113.1> where R represents a lower alkyl radical of 1 to 4 carbon atoms; cycloalkyl of 3 to 7 carbon atoms. bone; lower alkenyl; haloalkyl of 1 to 4 carbon atoms and of 1 to 3 halogen atoms independently selected from fluorine, chlorine, bromine and iodine atoms; haloalkenyl of 2 to 4 carbon atoms and of 1 to 3 halogen atoms independently selected from fluorine, chlorine, bromine atoms and iodine; lower alkoxy; lower alkylthio; lower alkoxyalkyl of which the alkoxy and alkyl parts independently have 1 to 3 carbon atoms; lower alkylthioalkyl, the alkyl parts of which independently have 1 to 3 carbon atoms; phenyl; naphth1-yl, inden-1-yl; 4-fluorophenyl; arylalkylene from 1 to 3 carbon atoms in the alkylene part and the aryl part of which is a phenyl naphth1-yl or inden-1-yl radical; or a substituted aryl or arylalkylene radical chosen from those of the formulas:  <EMI ID = 114.1>    <EMI ID = 115.1> where one, two or three of R, R, R, R, R and R9 are independently selected from the lower alkyl, lower alkoxy, halo, nitro and haloalkyl radicals having 1 to 3 carbon atoms and 1 to 2 - Compound according to claim 1, in the formula of which one of R and R represents a hydrogen atom or methyl, ethyl or propyl radical. 3 identical or different halogen atoms, the others being hydrogen atoms, and R represents a single bond or an alkylene radical of 1 to 3 carbon atoms,  <EMI ID = 127.1> alkyl of 1 to 4 carbon atoms, R2 represents a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl or alternatively R and R together with the nitrogen atom to which they are united form a saturated or unsaturated nitrogen heterocycle of 3 to 6 atoms in the ring, one of which is a nitrogen atom and the others of which are carbon atoms, X represents a hydrogen atom or a lower alkyl, lower alkoxy, halo or trifluoromethyl radical and can occupy any accessible position of the phenyl radical, and its compatible salts. 3 - Compound according to claim 1,  <EMI ID = 121.1> one methyl or ethyl radical and the other represents a hydrogen atom or methyl or ethyl radical. 3 identical or different halogen atoms, the others being hydrogen atoms, and R represents a single bond or an alkylene radical of 1 to 3 carbon atoms, <EMI ID = 116.1> alkyl of 1 to 4 carbon atoms,  <EMI ID = 117.1> alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, lower alkoxycarbonylalkyl, lower alkoxyalkyl or lower alkylthioalkyl or alternatively  <EMI ID = 118.1> they are united form a saturated or unsaturated nitrogen heterocycle of 3 to 6 atoms in the ring, one of which is a nitrogen atom and the others of which are carbon atoms, X represents a hydrogen atom or a lower alkyl, lower alkoxy, halo or trifluoromethyl radical and can occupy any accessible position of the phenyl radical and Y represents a lower alkyl, lower alkoxy, halo, lower halo-alkyl radical of 1 to 4 carbon atoms and from 1 to 3 identical or different halogen atoms, lower halo-alkoxy of 1 to 4 carbon atoms; cycloalkyl of 3 to 7 carbon atoms; lower alkenyl; haloalkyl of 1 to 4 carbon atoms and of 1 to 3 halogen atoms independently chosen from fluorine, chlorine, bromine and iodine; haloalkenyl of 2 to 4 carbon atoms and of 1 to 3 halogen atoms independently selected from fluorine, chlorine, bromine and iodine atoms; lower alkoxy; lower alkylthio; lower alkoxyalkyl of which the alkoxy and alkyl parts independently have 1 to 3 carbon atoms; lower alkylthioalkyl, the alkyl parts of which independently have 1 to 3 carbon atoms; phenyl; naphth1-yle; inden-1-yl; 4-fluorophenyl; arylalkylene from 1 to 3 carbon atoms in the alkylene part and the aryl part of which is a phenyl, naphth1-yl, or inden-1-yl radical; or a substituted aryl or arylalkylene radical chosen from those of the formulas:  <EMI ID = 125.1>    <EMI ID = 126.1> where one, two or three 'between,, R, R, R and R9 are independently selected from the lower alkyl, lower alkoxy, halo, nitro and haloalkyl radicals having 1 to 3 carbon atoms and 1 to 4 - Compound according to claim 1,  <EMI ID = 122.1> one has a hydrogen atom and the other represents a methyl, ethyl or propyl radical. 4 carbon atoms and from 1 to 3 identical or different halogen atoms or lower halo-alkylthio of 1 to 4 carbon atoms and from 1 to 3 identical or different halogen atoms, it being understood when Y is a halogen atom, then R, R <1> and R2 are not all hydrogen atoms and it is also understood that when Y is other than a trifluoromethyl radical, X is other  <EMI ID = 119.1> gene and R is a hydrogen atom, then R is a methyl, ethyl, propyl, 2-halophenyl, 2-  <EMI ID = 120.1> and its compatible salts. 5 - Compound according to claim 1, in the formula of which X represents a hydrogen atom. 6 - Compound according to claim 2, in the formula of which X represents a hydrogen atom. 7 - Compound according to claim 3, in the formula of which X represents a hydrogen atom. 8 - Compound according to claim 1, in the formula of which R represents a phenyl, naphth-1-yl, 4-fluorophenyl or substituted aryl radical. 9 - Compound according to claim 8, in the formula of which R represents a phenyl, naphthyl or monosubstituted phenyl radical. 10 - Compound according to claim 9, in the formula of which R represents a phenyl, halophenyl or alkyl (lower) phenyl radical. 11 - Compound according to claim 10, in the formula of which R represents a phenyl, 4-fluorophenyl, 2-halophenyl or 2- (lower alkyl) phenyl radical. 12 - Compound according to claim 11, in the formula in which X represents a hydrogen atom and R and R each independently represent a hydrogen atom or methyl or ethyl radical. 13 - Compound according to claim 1, in the formula of which R represents a lower alkyl, cycloalkyl, lower alkenyl, haloalkyl or halo-alkenyl radical. 14 - Compound according to claim 13,  <EMI ID = 123.1> smells of a hydrogen atom or methyl or ethyl radical and the other represents a methyl or ethyl radical. 15 - Compound according to claim 14, in the formula of which R represents a methyl, ethyl or propyl radical. 16 - Compound according to claim 15, in the formula in which one of R and R represents a hydrogen atom and the other represents a methyl or ethyl radical. 17 - Compound according to claim 16, in the formula of which X represents a hydrogen atom. 18 - Compound of formula:  <EMI ID = 124.1> where R represents a lower alkyl radical from 1 to 19 - Compound according to claim 18,  <EMI ID = 128.1> each a hydrogen atom or a methyl or ethyl radical. 20 - Compound according to claim 19,  <EMI ID = 129.1> one methyl or ethyl radical and the other represents a hydrogen atom or methyl or ethyl radical. 21 - Compound according to claim 18, in the formula in which one of R <1> and R2 represents a methyl or ethyl radical and the other represents a hydrogen atom. 22 - Compound according to claim 19, in the formula in which X represents a hydrogen atom and R represents a phenyl, naphthyl, 4fluorophenyl, 2-halophenyl or 2- (lower alkyl) phenyl radical. 23 - Compound according to claim 22,  <EMI ID = 130.1> one hydrogen atom and the other represents a hydrogen atom or methyl or ethyl radical. 24 - Compound according to claim 23, in the formula of which R represents a phenyl, 2-fluorophenyl, 2-chlorophenyl or 2-methylphenyl radical. 25 - Compound according to claim 23, in the formula of which R represents a phenyl radical. 26 - Compound according to claim 23, in the formula of which R represents a phenyl radical and one of R and R represents a hydrogen atom and the other represents a methyl radical. 27 - Compound according to claim 23, in the formula of which R represents a phenyl radical and one of R and R represents a hydrogen atom and the other represents an ethyl radical. 28 - Compound according to claim 18, in the formula of which R represents a lower alkyl, cycloalkyl, lower alkenyl, halo-lower alkyl or lower halo-alkenyl radical. 29 - Compound according to claim 28, in the formula of which R <1> and R2 each independently represent a hydrogen atom or a methyl or ethyl radical. 30 - Compound according to claim 29, in the formula of which R represents a methyl, ethyl or propyl radical. 31 - Compound according to claim 30, in the formula in which one of R <1> and R2 represents a hydrogen atom and the other represents a methyl or ethyl radical and X represents a hydrogen atom. 32 - A compound according to claim 29, in the formula of which X represents a hydrogen atom. 33 - Compound according to claim 18, in the formula of which X represents a hydrogen atom. 34 - Compound according to claim 1, in the formula of which X represents a hydrogen atom. 35 - Compound according to claim 34, in the formula of which Y represents a lower haloalkyl radical of 1 or 2 carbon atoms. 36 - Herbicidal composition, characterized in that it comprises in effective herbicidal amount a compound according to claim 1 or a mixture such compounds and a compatible excipient. 37 - Herbicidal composition, characterized in that it comprises in effective herbicidal amount a compound according to claim 25 or a mixture such compounds and a compatible excipient. 38 - Process for preventing the appearance of plants or for destroying them, characterized in that an effective herbicidal amount is applied to a compound according to claim 1 or a mixture of such compounds on the foliage or the potential growth medium of these plants . 39 - Process for preventing the appearance of plants or for destroying them, characterized in that an effective herbicidal amount is applied to a compound according to claim 25 or a mixture of such compounds on the foliage or the potential growth medium of these plants . 40 - Composition for regulating plant growth, characterized in that it comprises, in an amount suitable for modifying the growth rate of plants, a compound according to claim 1 or a mixture of such compounds. 41 - Process for regulating the growth of plants, characterized in that a compound according to claim 1 is applied to the foliage of these plants or their growth medium, in a quantity suitable for modifying the growth rate of these plants or a mixture of such compounds. 42 - Process for the preparation of the compound according to claim 1, in which R represents a phenyl, naphth-1-yl, inden-1-yl or substituted aryl radical as defined in claim 1, characterized in that we put the corresponding compound of formula:  <EMI ID = 131.1> where X and Y are as defined in claim 1 and Z 'corresponds to the desired aryl or substituted aryl radical R, in contact with a halogen chosen from chlorine, bromine and iodine and with a liquid carboxylic acid under reaction conditions so as to obtain the corresponding compound of formula I. 43 - Process according to claim 42, characterized in that it is carried out in an inert organic solvent at temperatures of about 0 to 100 [deg.] C and the halogen is bromine. 44 - Process according to claim 43, characterized in that the inert organic solvent is an excess of the liquid carboxylic acid, 45 - Process for the preparation of a compound according to claim 1, in substance as described above.