CH619697A5 - Process for the preparation of an aralkylimidazole substituted in position 1 - Google Patents

Abstract

A compound of formula: <IMAGE> is prepared by reaction of an (XI)aI-substituted imidazole, of its derivative or of its salt with a compound of formula (see formula at the top of page 2). The meaning of the symbols is given in Claim 1. The compounds obtained can be used as fungicidal agents.

Description

       

  
 

** ATTENTION ** start of the DESC field may contain end of CLMS **. 

 



   CLAIMS
 1.  Process for the preparation of an aralcoylimidazole substituted in position 1, of formula:
EMI1. 1
 in which
 Z1 is a C6 to C14 aryl radical or a substituted C6 to C14 aryl radical;
   R1 is a hydrogen atom, a C1 to C10 alkyl radical; a C2 to C12 alkenyl radical; a C7 to C9 aralkyl radical which may be substituted; a phenyl radical which may be substituted, a C3 to C7 cycloalkyl radical, OR a C5 to C7 cycloalkenyl radical;
   R2 is a C1 to C1o alkyl radical, a C2 to C12 alkenyl radical, a C7 to C9 aralkyl radical which may be substituted;

   a phenyl radical which may be substituted;
 RIÚ and R?, Taken together, can form a C3-C8 cycloalkyl radical;
 A and B are divalent C1 to C5 alkylene radicals;
 X1 is a C1 to C4 alkyl radical, a halogen atom or a nitro radical;
 al is an integer from 0 to 3;
 n is an integer equal to 0 or 1 n 'is an integer equal to 0 or 1;

   and the sum of n + n 'is 1 or 2;
 or, when ZI is an unsubstituted phenyl radical, RIÚ is a hydrogen atom, A is methylene, and n 'is O, then R? is a C4 to C10 alkyl radical, a C2 to C12 alkenyl radical, a C7 to Cg aralkyl or C7 to Cg aralkyl radical, a phenyl or substituted phenyl radical, a cycloalkyl radical
C3 to C7 OR a C5 to C7 cycloalkenyl radical; with the condition that, when R1 and R, 2 are both hydrogen, n + n 'is 1 or 2;

   and with the additional condition that, when ZI is phenyl (C6H5) and RIÚ, RIê and RI are hydrogen, RI4 is different from a C1 to C3 alkyl, and the addition salts with agronomically acceptable acids of the derivatives in question , characterized in that a derivative of formula is reacted
EMI1. 2
 in which W is a halogen, a C1 to C4 alkyl sulfonate, benzenesulfonate or toluenesulfonate, and ZI, A, n, RIÚ to R ?, B and n 'are as defined above with an appropriate imidazole derivative or a salt of this derivative. 



   2.  Process according to claim 1, characterized in that the said imidazole derivative or the salt of this derivative is used in substantially equimolecular amounts or in excess relative to the equimolecular amount. 



   3.  Process according to claim 2, characterized in that the reaction is carried out in an inert solvent. 



   4.  Process according to claim 1, characterized in that the imidazole derivative of formula III is reacted with a metal salt in the form of a free base or of an addition salt with an acid to obtain a complex metal salt of formula
EMI1. 3
 in which the substituents Z ,, R1 to R ?, A, B, XI, n, n 'et al have the same meanings as in formula III above, M is a metal cation which can be chosen from groups IIA , IVA,
VA, IB, IIB, VIA, VIIA and VIII of the periodic table, Y is a solubilizing antagonist anion and m is a number from 1 to 4. 



   5.  Use of the alkyllimidazole derivative obtained according to claims 1 and 4, as a fungicidal agent. 



   6.  Aralkoylimidazole substituted in position 1, obtained by the process according to claim 1. 



   The invention relates to a process for the preparation of an aralkoylimidazole substituted in position 1 and to its application as a fungicidal agent. 



   This substituted aralcoylimidazole corresponds to the formula:
EMI1. 4
 in which
 Z1 is a C6 to C14 aryl radical or a substituted C6 to C14 aryl radical;
 RIÚ is a hydrogen atom, a C1 to C10 alkyl radical; C12 to C12 unradicalalkenyl; a C7 to C9 aralkyl radical which may be substituted; a phenyl radical which may be substituted, a C3 to C7 cycloalkyl radical, or a C5 to C7 cycloalkenyl radical;
   R? is a C1 to C1o alkyl radical, a C2 to C12 alkenyl radical, a C7 to Cs aralkyl radical which may be substituted;

   a phenyl radical which may be substituted;
   R1 and R2, taken together, can form a C3 to C8 cycloalkyl radical;
 A and B are divalent C1 to C5 alkylene radicals;
 X1 is a C1 to C4 alkyl radical, a halogen atom or a nitro radical;
 ai is an integer from O to 3;
 n is an integer equal to O or 1; n 'is an integer equal to o or 1;

   and the sum of n + n 'is 1 or 2;
 or, when Z, is an unsubstituted phenyl radical, RIÚ is a hydrogen atom, A is methylene, and n 'is O, then R? is a C4 to C1O alkyl radical, a C2 to C12 alkenyl radical, a C7 to C9 aralkyl or C7 to C6 substituted aralkyl radical, a phenyl or substituted phenyl radical, a C3 to C7 cycloalkyl radical or a C3 to C7 cycloalkenyl radical; with this condition that, when RIÚ and R? are both hydrogen, n + n 'is 1 or 2;

   and with the additional condition that, when ZI is phenyl (C6H8) and Rt, RIê and R31 are hydrogen, Rt is different from C1 to C3 alkyl and the addition salts with agronomically acceptable acids of the derivatives in question.   



   This process is characterized in that a derivative of



  formula
EMI2. 1
 in which W is a halogen, a C1 to C4 alkyl sulfonate, benzenesulfonate or toluenesulfonate, and Z ,, A, n, RIÚ to R ?,
B and n 'are as defined above, with an appropriate imidazole derivative or a salt of this derivative. 



   Another subject of the invention is the application of this substituted alkyllimidazole as a fungicidal agent, as such or in the form of an addition salt with agronomically acceptable acids. 



   It is also possible to produce mixtures of: A) at least one compound of formula III above or of addition salts with acids of these compounds, and B) at least one metal salt capable of forming a complex with said compounds or salts and / or a fungicidal agent containing at least one metal. 



   The metal salt complexes can be prepared by contacting in a suitable medium, usually a solvent, a suitable metal salt and a suitable imidazole derivative in the form of the free base or addition salts with acids.  The preparation of imidazole precursors is described in more detail in the following description. 



   In the compounds of formula III above, the aryl or aralkyl heterocyclic substituents can be phenyl, naphthyl,
 biphenyl, acenaphthenyl, indanyl, indolyl, pyridyl, pyrimidyl, pyrryl, furyl, thienyl, methylenedioxyphenyl, benzyl, phenethyl or naphthylmethyl as the case may be. 



   The term alkyl is used to denote an alkyl radical comprising
 7 to 9 carbon atoms, preferably a benzyl, phenethyl or naphthylmethyl radical, or a benzyl, phenethyl or
   naphthylmethyl substituted with up to three selected substituents
 independently from the group consisting of fluoro, chloro,
 bromo, iodo, nitro, amino, cyano, methylthio, methoxy, trihalo
 genomethyl, a radical containing from 1 to 4 carbon atoms and
 in particular a methyl or ethyl radical;
 the term cycloalkyl is used to designate a C 9 -C 9 cycloalkyl radical, and
 the term cycloalkenyl is used to denote a C5 to Ce cycloalkenyl radical.    



   By the term substituted phenyl as used in the definition of RIÚ and R ?, should be understood a phenyl radical which can be substituted with up to two substituents chosen from the group consisting of C1 to C4 alkyl, methoxy , ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthio and the like. 



   Other compounds which can be taken into consideration are complexes of metal salts of the above-mentioned aralkyllimidazoles substituted in position 1, complexes which can be represented by the following formula (IV):
EMI2. 2
 in which Zl, A, B, Rl, R21, n, n ', XI, and q are as defined for formula (III) above, and M is a metal cation which can be chosen from groups IIA , IVA, VA, IB, IIB, VIB, VIIB and VIII of the periodic table of elements according to American standardization (respectively groups 2a, 4b, Sb, lb, 2b, 6a, 7a and 8 according to French standardization); Y is a solubilizing antagonist anion, and m is a number from 1 to 4.    



   These aralcoylimidazoles substituted in position 1 have destructive fungicidal properties which are unique in that they kill phytopathogenic fungi in infected plant tissues and are therefore usable after a fungal infection has already been declared.  The teletoxic properties of these compounds are also unique due to the fact that the compounds in question are capable of moving both acropetally and basipetally in the tissues of plants.  In addition, these compounds have protective properties against phytopathogenic fungi when applied to plants before infection. 



   The preferred compounds of the group indicated above are those in which n ', in formulas (III) and (IV), is equal to 1.  The compounds more especially preferred from those of said group are those in which n 'is equal to 1 and n is equal to O.  The compounds considered to be the most advantageous among those of the group in question are those in which n 'is equal to 1, n is equal to O;

  RIÚ is a hydrogen atom; al is 0; Z, is a substituted phenyl radical containing up to three substituents chosen from the group consisting of C1 to C4 alkyl, methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro amino, methylthio, and R? is a C4 to C1 alkyl radical, a C2 to C12 alkenyl radical, a C7 to C9 aralkyl radical which can be substituted with up to two substituents chosen from the group consisting of C1 to C4 alkyl, methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino and methylthio; a phenyl radical which can be substituted with up to two substituents chosen from the group consisting of C1 to C4 alkyl, methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino and methylthio;

   a C3 to C7 cycloalkyl radical or a C, to C7 cycloalkenyl radical. 



   Among typical compounds included in the scope of the invention, there may be mentioned in particular: l- [P- (2,4-dichlorophenyl) hexyl] imidazole 1- [ss- (2-chlorophenyl) hexyl] imidazole 1- [ss - (4-bromophenyl) hexyl] imidazole 1- [ss- (3-iodophenyl) hexyl] imidazole l- [P- (2,6-dichlorophenyl) decyl] imidazole 1 - [ss42,4-dichlorophenyl) -ss4p-chlorophenyl ) ethyl] imidazole 1 - [α;-( 2,4-dichlorobenzyl) pentyl] imidazole 1- [ss- (2,4-dichlorobenzyl) hexyl] imidazole 1 - [ss42-methyl-4'-chlorophenyl) heptyl] imidazole 1 - [ss- (2, 4-dichlorophenethyl) hexyl] imidazole 1- [ss- (2,4-dichlorophenyl) nonyl] imidazole 1 - [ss42,4-dimethylthiophenyl) hexyl] imidazole 1- [ss- (4-nitrophenyl) hexyl] imidazole 1- [ ss- (3,4-dichlorophenyl) hexyl] imidazole 1- [ss- (tolyl) hexyl] imidazole l-CP- (4-anisyl) hexyl] imidazole 1- [ss- (2,4-dichlorophenyl) -ss- cyclopropylethyl] imidazole 1 - [ss42,4-dichlorophenyl> ss-cyclopentylethyl] imidazole 1 - [ss42,4-dichlorophenyl) -ss-cycloheptylethyl] imidazole 1- [ss, ss-trimethylene-ss- (2 ', 4-dichlorophenyl ) ethyl] imidazole 1- [ss, ss-pentamethylene-ss- (2 ', 3'-dibromophenyl) ethyl] -imidazole 1- [ss, ss-heptamethylene-ss- (3', 5'-difluorophenyl) ethyl] imidazole. 

 

   The above-mentioned compounds can be prepared by using normal synthetic methods.  Among the typical preparation methods which can be used to prepare the compounds of formula III are the following general syntheses. 



  1- (ss-alcoylsubstituted) imidazole
 When the suitable acetate type derivative (II) is allowed to react with sodium hydride in tetrahydrofuran (THF) or in glyme, the corresponding sodiosel is formed (VIII).  The reaction of (VIII) with an organic halide gives the ester (IX).    



   The set of specified reactions can be represented as follows:
 (See next page)
EMI3. 1

 These esters (IX) are converted into the corresponding carbinol derivatives (X) by reduction using reagents such as lithium aluminum hydride (LiAIH4) in ether or bis- (2-methoxyethoxy) aluminum in benzene.  The subsequent treatment of (X) with methanesulfonyl chloride in the presence of triethylamine in a solvent of the aromatic hydrocarbon type such as benzene or toluene provides the sulfonate (XI).  A treatment of (X) with thionyl chloride or with phosphorus pentachloride in a solvent of the aromatic hydrocarbon type
 that benzene or toluene provides chloride (XIa). 

  The reaction
 of (XI) with an excess of an imidazole or the reaction of (XIa) with the sodium salt of an imidazole either as it is or in the presence of solvents such as benzene, glyme, N, N-dimethylformamide, etc. , gives the alkylated imidazole products (XII).    



     I- (ol-alkyl substituted) imidazole
 The imidazoles x-substituted with alkyl in position 1 are synthesized by a different route, which can be schematically represented as follows:
EMI3. 2
  
 Grignard's reagent (XIII) is formed by reacting metallic magnesium with the appropriate organic chloride in ether.  This reagent (XIII) is then allowed to react with the desired aldehyde to give the carbinol derivative (XIV).  The formation of the sulfonate or of the chloride, followed by its reaction with an imidazole or with its sodiosel by using the synthetic route described above, gives the product (XV). 



  Extension of the methylene chain - Malonate pathway
 A synthesis passing through the malonate is used to arrive at the raw materials for some other closely related analogs when the methylene chain is extended. 
EMI4. 1




   The reaction of an alkyl halide (XVI) with sodioethyl malonate in a solvent such as THF or glyme gives the substituted malonate (XVII).  A further reaction of (XVII) with first sodium hydride in THF, then by addition of the appropriate organic halide provides the disubstituted ester (XVIII). 



  Basic hydrolysis of (XVIII) followed by acidification and decarboxylation gives the monoacid (XIX).  The reduction of (XIX) by LiAIH4 gives the corresponding carbinol derivative (XX). 



  The final product, alkylated imidazole (XXI), is then formed in the usual way. 



  Extension of the methylene chain
 The methylene chain can be extended from methanesulfonate (XI) through the preparation of nitrile (XXII):
EMI4. 2
  
 This sulfonate (XI) in DMF is treated with sodium cyanide in DMF to give the derivative of the nitrile type (XXII). 



  Hydrolysis of (XXII) in boiling 50% sulfuric acid gives acid (XXIII) which is then reduced using LiAIH4 to give alcohol (XXIV).  The imidazole derivative is then formed by passing through the sulfonate by operating in the usual manner, or else the sulfonate can be recycled by repeating the operation to carry out a new chain extension. 



  Phenyl analogs
 The synthesis of the substituted phenyl analog involves a Darzens reaction.  A substituted benzophenone is reacted with ethyl chloroacetate in the presence of sodium hydride to give the glycidic ester (XXV) as follows:
EMI5. 1

 Hydrolysis and subsequent decarboxylation of (XXV) gives diarylacetaldehyde (XXVI).  This aldehyde (XXVI) is reduced to the corresponding alcohol (XXVII) by LiAIH4 which is then converted in the usual manner to finally obtain the imidazole derivative constituting the desired product (XXVIII). 



  Alcoylimidazole a, ss-disubstituted
 The Friedel-Craft acylation, with an acyl halide, of an aromatic hydrocarbon substituted in the presence of aluminum chloride either as it is or with a halogenated hydrocarbon, provides the desired product by operating in a schematic manner as follows:
EMI6. 1

 The treatment of (XXIX) with an excess of ethyl chloroacetate and sodium hydride gives the glycidic ester (XXX) which, by saponification with a base and hydrolysis with a hot mineral acid, then decarboxylation, gives the aldehyde (XXXI).  A reaction from
Grignard with an alkyl- or arylmagnesium halide gives alcohol (XXXII).  The formation of the sulfonate, followed by its reaction with an imidazole, operating in the manner already described above, gives the desired product (XXXIII). 



  Imidazole ss, ss-alcoyidisubstituted
 When the appropriate sodioalkyl acetate derivative (XXXIV), prepared as described above, is allowed to react at elevated temperatures in a solvent such as ether, tetrahydrofuran or dimethylformamide with an iodoalkane, obtains the desired trisubstituted acetate (XXXV), the reduction of which by LiAIH4 in anhydrous ether gives alcohol (XXXVI).  The formation of the sulfonate, then the reaction with an imidazole by operating according to the principle-already described above, finally gives the desired product (XXXVII). 

  This succession of reactions can be schematized as follows
EMI6. 2

EMI6. 3
  
EMI7. 1

Other synthetic routes leading to phenyl analogs
 Reduction of a substituted phenylacetic acid (XXXVIII) using LiAIH4 as a reducing agent in tetrahydrofuran gives alcohol (XXXIX).  Then continue as before (sulfonate, then reaction with an imidazole derivative) product (XL). 
EMI7. 2


 

  Imidazole l- (ss-diarylalcoylsubstituted)
 The reaction of chloroacetaldehyde / diethylacetal with a substituted aromatic hydrocarbon, operating in the presence of sulfuric acid at room temperature, gives substituted arylethyl chloride (XLI).  The reaction of (XLI) with the sodium salt of an imidazole derivative as described above finally gives the desired product (XLII). 
EMI7. 3
  



     1 - [# - (substituted aryl) hexyl] imidazole
 When a substituted aromatic hydrocarbon is treated with 1,2-epoxyhexane in the presence of aluminum chloride, hexane (XLIII) is obtained as follows:
EMI8. 1

 The formation of methanesulfonate, followed by a reaction with an imidazole derivative, gives the desired product (XLIV). 



   When a benzene substituted with electron-donating radicals is treated with 1,2-epoxyhexane in the presence of stannic chloride, hexanol (XLV) is obtained:
 The imidazole derivative is formed via the sus route
 specified involving the formation of a methanesulfonate. 
EMI8. 2




  1- [ss- (phenylalkylthio- or alkylsulfonylsubstituted) alkyl] imidazoles
 The alkylthio- and alkylsulfonyl- derivatives are prepared from the aldehyde (XLVI). 
EMI8. 3
  
EMI9. 1




   Aldehyde (XLVI) is reduced to alcohol (XLVII) with LIAIT4.    



  The alcohol (XLVII) is reacted with methanesulfonyl chloride in the presence of triethylamine to form the sulfate (XLVIII).  Treatment of methanesulfonate (XLVIII) with sodium cyanide gives the benzylnitrile derivative (XLIX).  Alkylation of the nitrile (XLIX) by means of metallation with NaH, followed by treatment with an alkyl halide, gives the derivative of alkylbenzylnitrile (L).  Hydrolysis of the nitrile (L) with sulfuric acid in an alcoholic solvent gives ar-alkylphenylacetic acid (LI) to remain which, by steep reduction of
LiAIH4, gives phenethyl alcohol (LII).  The product of the imidazole derivative type is formed by passing through methanesulfonate, according to the principle of synthesis already used above. 

  When the imidazole derivative (LIII) is oxidized with hydrogen peroxide in acetic acid, the alkylsulfonyl derivative (LIV) is formed
EMI9. 2

Nitrosubstituted phenyl derivatives (LVI) are formed by nitration of unsubstituted or substituted analogs (LV):
EMI9. 3

The amino substituted phenyl derivatives (LVII) are formed by reduction of the nitrosubstituted phenyl derivative (LVI). 
EMI9. 4

 The derivatives in which the imidazole ring itself is substituted (LIX) are prepared by reacting the appropriate methanesulfonate (LVIII) with either an excess of substituted rimidazole or the sodium salt of the imidazole:

  :
EMI9. 5
  
Addition salts with acids
EMI10. 1

 The addition salts are prepared, with an acid, of the derivatives of the aralkoylimidazole type by treating an ethereal solution of imidazole (LX) with an equivalent proportion of the desired mineral or organic salt dissolved in ether or in alcohol, after which it is filtered or concentrated, then filtered to obtain the desired salt (LXI). 
EMI10. 2




   The complex metal salts of the derivatives of the type are prepared
 aralcoylimidazole (LXII) by the treatment of an alcoholic solution
 or aqueous rimidazole in question (LX) with a metal salt
 at temperatures between about 15 and about 60 C.    



   Below are given various examples intended to illustrate
 various embodiments of the invention.  We use abbreviations
 M (for mole) and mM (for millimole) to designate quan
 substances. 



   Example 1:
 I - [I32,4-dichiornphenyI) hexyl] imidazole
 1.  Ethyl-ss- (2,4-dichlorophenyl) hexanoate: 58.6 g
 (1.22 M) 50% sodium hydride in 1 I of tetrahydrofuran
 (THF) anhydrous, 50.0 g (215 mM) of ethyl acetate are added at 40 ° C.
   2,4-dichlorophenyl, and the mixture is stirred for 10 min.  When
 the release of H2 begins, the temperature is lowered
 reaction up to 10 C, and 200.0 g (858 mM) are added dropwise
 additional ester.  When this addition is completely finished, the reaction mixture is continued to stir, leaving it to
 warm up to room temperature.  It is then heated to
 40 C for 1 h, then cooled to temperature
 ambient. 

  To this mixture, 198.0 g (1.076 M) of
 l-iodobutane and, when this addition is completely complete,
 the reaction mixture is stirred at 40 ° C. for 16 h.  We cool
 the mixture, the volume is reduced by distillation, and it is poured into 1.5 l of water.  The insoluble oil is separated, and the aqueous layer is extracted with ether.  The ethereal extract is combined with the oil. 



   The ethereal solution is washed with 100 ml of dilute hydrochloric acid, then with 100 ml of sodium bicarbonate solution, and finally with 100 ml of water.  The solution is dried, concentrated, and 324.3 g of crude product are thus obtained.  Distillation of this crude product gives 223.0 g (72%) of pure ester (115-20 "C / 0.25 mm).  The substance is identified by infrared and its purity is determined by chromagography. 



   2.    2- (2,4-dichlorophenyl) hexan-1-ol: to 11.7 g (308 mM) of lithium aluminum hydride in 1 1 of anhydrous ether at 5-10 C, 140 are added slowly 0.0 g (486 mM) ethyl-B- (2,4-dichlorophenyl) hexanoate prepared as described above.  When the addition is completely complete, the reaction mixture is further stirred and allowed to warm up slowly to room temperature.  The suspension is slowly added to ice water while H2 gas is given off vigorously.  When this addition is completely finished, the mixture is acidified with concentrated hydrochloric acid.  An organic layer is formed which is separated, and the aqueous layer stiff with ether is extracted. 

  This extract is combined with the organic layer, and the solution is washed with water, then with a dilute solution of sodium bicarbonate.  After drying over anhydrous magnesium sulfate, the ethereal solution is concentrated, then the residue is distilled (118-23 "C / 0.2 mm), which gives 110.8 g (92%) of product. 



   3.    2- (2,4-Dichlorophenyl) hexyl methanesulfonate: 24.7 g (0.1 M) 242.4-dichlorophenyl) hexan-1-ol and 13.8 g (0.12 M) chloride chloride methanesulfonyl in 200 ml of benzene at 10 ° C., 14.2 g (0.14 M) of triethylamine are slowly added.  When the addition is completely complete, the reaction mixture is stirred and allowed to warm to room temperature over a period of 30 min.  The suspension is then heated to reflux for 30 min, cooled and poured into water.  The organic solution is washed with dilute hydrochloric acid, then with water, and finally with a dilute solution of sodium bicarbonate. 

  After drying over anhydrous magnesium sulfate, the benzene is removed by distillation, which gives 31.8 g (98%) of the crude product which is identified by infrared and by nuclear magnetic resonance.  Its purity is determined by chromatography. 



   4.  Imidazole reaction: at 27.2 g (0.4 M) of imidazole at 90 ° C., 31.8 g (98 mM) of 242.4-dichlorophenyl) hexyl methanesulfonate added as described are added above, and the mixture is stirred at 95 ° C for 16 h.  At the end of this period, the reaction mixture is cooled and poured into 500 ml of water.  After stirring for 1 h, the organic material is separated, and the aqueous layer is extracted with ether.  The ethereal extract is combined with the organic phase and, after washing with water, it is dried and concentrated, which gives 24.4 g (88%) of product of the imidazole type which is identified by infrared, by nuclear magnetic resonance and by elemental analysis.  

  Its degree of purity, greater than 95%, is determined by chromatography. 



  Example 2:
 I - [P2,4-dichlornphenyl) hexyl] imidazole hydrochloride
 In 30.0 g (10 mM) of 1- [ss42,4-dichlorophenyl) hexyl] - imidazole dissolved in 200 ml of ether, dry hydrochloric gas is bubbled until the mixture is acidic with sunflower.  A colorless solid is formed which is separated by filtration; 24.5 g of the desired salt (hydrochloride) are thus obtained, which is identified by nuclear magnetic resonance. 



  Example 3:
 L- [ss42,4-dichlorophenyl) hexyl] imidazolezinc chloride
 Method A: To a solution of 2.0 g (6.7 mM) of 1- [ss42,4- dichlorophenyl) hexyl] imidazole in 10 ml of absolute ethanol, a solution of 0.46 g is added dropwise (3.6 mM) of zinc chloride in 30 ml of absolute ethanol.  The reaction mixture is stirred at room temperature for 10 min, and the solvent is removed in vacuo.  A white glassy solid is isolated as a product, and identified by nuclear magnetic resonance. 



   Method B: 2.0 g (6.7 mM) of 1- [ss42,4-dichlorophenyl) hexyl] imidazole and 0.92 g (6.7 mM) of zinc chloride are mixed in 40 ml of an acetone: methanol: water solvent system (1: 1: 2).     This preparation is immediately applied to the foliage of plants. 



  Example 4:
 1- [ss-2,4- (dichlorophenyl) hexyl] imidazole oxalate
 To a solution of 4 g 13.5 mM) of 1- [ss- (2,4-dichlorophenyl) - hexyl] imidazole in ether, a solution of 1.7 g (13.5) is added dropwise mM) of oxalic acid dissolved in 10 ml of methanol.  A white precipitate immediately forms.  This precipitate is collected by filtration and dried under vacuum, which gives 3.37 g of a solid, P. F.    126-128 C.    



  Example 26:
 1- [ss- (p-methylthiophenyl) hexyl] imidazole
 1.  p-methylthiophenylmethanol: to 19.8 g (521 mM) of lithium aluminum hydride (LiAIH4) in 750 ml of anhydrous ether, 98 g (640 mM) of p-methylmercaptobenzaldehyde are added slowly in 250 ml of anhydrous ether at a temperature below 10 "C.    



  When Addition is completely finished, the reaction mixture is stirred for 30 min at 10 ° C., then the reaction is stopped by slowly adding 100 ml of acetone to remove the unreacted LiAIH4. 



   To this mixture is added 500 ml of water, and the reaction mixture is acidified by the addition of concentrated hydrochloric acid.  The ethereal layer is separated, dried over anhydrous magnesium sulphate, then concentrated; 89.6 g of the crude product are thus obtained.  This residue is recrystallized from ether / hexane, which gives 75.8 g,
P. F.    38-40 C (yield 76%). 



   2.    p-methylthiophenylacetonitrile: to 73.0 g (470 mM) of p-methylthiophenylmethanol and 59.6 g (520 mM) of methanesulfonyl chloride in 250 ml of benzene, 59.6 g (590 mM) of triethylamine are slowly added to the during a period of 1 hour to a
 temperature below 15 "C.     When the bill is completely
 finished, the reaction mixture is stirred for 1 h and left
 warm up to room temperature. 



   The reaction mixture is combined with 400 ml of dilute hydrochloric acid.  The benzene layer is separated, washed with 250 ml of water, dried and concentrated; 74.7 g are thus obtained
 of the crude product of the mesylate type. 



   This residue is added to 25.5 g (520 mM) of sodium cyanide in
 300 ml of dimethyl sulfoxide, and the mixture is stirred for 1 h.  We pour the
 reaction mixture in ice water; a solid of
   yellow tint which is collected by filtration and which is recrystallized
 ser from benzene / hexane, which gives 60.8 g (79%) of the product,
 P. F.    44-5 C.    



   3.  2- (p-methylthiophenyl) hexanenitrile: to 12.5 g (250 mM)
 50% sodium hydride in 300 ml of tetrahydrofuran
 (THF) anhydrous, distilled, 60.0 g (258 mM) of p-methyl are added
 thiophenylacetonitrile over a 1 hour period.  We shake it
 reaction mixture for 1 h, then added slowly
 48.8 g (265 mM) of 1-iodobutane.  When the bill is complete
 When finished, the reaction mixture is stirred for 2 h.  We
 combine said mixture with 500 ml of water, separate the organic phase, wash with water, then concentrate and thus obtain 80.1 g of crude product.  By distillation, 65.7 g (85%) of the product (126-30 C / 0.01 mm) are isolated. 



   The imidazole derivative is then prepared by the method described in Example 26, parts 2, 3,4 and 5. 



  Example 27:
 1- [ss- (p-methylsulfonylphenyl) hexyl] imidazole
 To 7.0 g (21 mM) of the nitric acid salt of 1- [ss4p-methylthio-phenyl) hexyl] imidazole in 75 ml of glacial acetic acid, dropwise added at a temperature below 10 ° C. 8.0 g (83 mM) 30% hydrogen peroxide.  When the addition is completely complete, the reaction mixture is stirred for 1 hour, heated on a steam bath for a second hour, then poured into ice water.  The solution is made basic to sunflower with sodium hydroxide, then the product is extracted with ether. 



   The ether extract is treated with nitric acid; the salt separates in the form of an oil.  This substance is treated with an aqueous solution of sodium hydroxide, and the product is thus obtained. 



  Extraction with ether and concentration of the extract gives 2.1 g (25%) of the methylsulfonylated derivative. 



  Example 29:
 1- [ss- (p-nitrophenyl) hexyl] imidazole
 To a mixture of 20 ml of nitric acid and 10 ml of sulfuric acid at 5 ° C., 10.0 g (44 mM) of l- [I3-phenylhexyl] imidazole in 10 ml of sulfuric acid are slowly added .  As soon as the addition is completely finished, the reaction mixture is poured into ice water; the oily product separates.  The acidic solution is decanted, the remaining oil is washed with water, then made basic with a dilute solution of sodium hydroxide. 



  The product is extracted with ether, the extract is dried and treated with nitric acid to precipitate the salt.  The salt is recrystallized from acetone / ether, which gives 4.8 g, P. F.  98-100 C. 



  Treatment of the salt with a dilute solution of sodium hydroxide gives the product in the form of a free base. 



  Example 30:
 1- [ss- (p-aminophenyl) hexyl] imidazole
 To 5.0 g (18.3 mM) of 1- [ss4p-nitrophenyl) hexyl] imidazole in 50 ml of methanol, 2.0 g of concentrated hydrochloric acid are added.  The solution is heated to reflux and four portions of 1 g of iron filings are added thereto at 5 min intervals.  When the additions are completely finished, the reaction suspension is stirred at reflux for 14 h.  The reaction mixture is cooled, then poured into water.  The organic material is extracted with toluene, then the extract is dried and concentrated, giving 4.5 g of crude product. 



   The oil is dissolved in ether, and the solution is treated with nitric acid.  The salt separates in the form of an oil.  The oil is treated with a dilute solution of sodium hydroxide, then extracted with ether; the extract is dried, then concentrated and 3.5 g of the imidazole derivative are thus obtained. 

 

  Example 31:
 1- [ss- (2,4-dichloro-5-nitrophenyl) hexyl] imidazole
 To a solution of 40 ml of nitric acid and 10 ml of sulfuric acid is added, at a temperature below 5 ° C., a solution of
 14.8 g (49.8 mM) of 1- [ss- (2,4-dichlorophenyl) hexyl] imidazole in 30 ml of sulfuric acid.  The reaction mixture is stirred for 30 min, then poured into ice water.  It separates an oily solid which is isolated by decantation from the dilute acid solution.  The residue is washed and then treated with an ammonium hydroxide solution. 



   The organic product is extracted with ether, the extract is dried and then treated with dry hydrochloric gas.  The salt (hydrochloride) precipitates, and it is separated by filtration, which gives 9.4 g of the crude product. Recrystallization of 2.7 g of this product from methanol gives 1.8 g of purified hydrochloride, P. F.    99-100 C.    



  Example 46:
 1- [ss- (2,4-dimethylphenyl) hexyl] imidazole
 1.    242,4-dimethylphenyl) hexan-1-ol: to a stirred mixture, at 0 ° C, of 173 g (1.63 M) of m-xylene and 78.0 g (0.30 M) of anhydrous stannic chloride through which a stream of nitrogen is constantly passed, 30.0 g (0.30 M) of 1,2-epoxyhexane in 50 g of m-xylene are added dropwise.  The reaction being exothermic, the reaction mixture heats up and the temperature is maintained.
 temperature at 3 C by the rate of addition.  After the addition is completely complete, the reaction mixture, which then contains
 223 g (2.0 M) of xylene, is stirred for 30 min at 0 C then is
 poured into ice-cold concentrated hydrochloric acid. 

  He separates a
 aqueous layer and an organic layer.  After extraction of the
 stiff aqueous layer of ethyl ether, combining the ethereal extract
 with the organic layer.  This organic solution is washed successfully
 sively with water, then with an aqueous bicar solution
 sodium bonate, and again with water.  The soil mixture
 Dried organic vants (ethyl ether and excess unreacted m-xylene) is then removed on a rotary evaporator.  We
 a concentrated residue is thus obtained which is subjected to fractional distillation under vacuum.  We prove, by spectral analysis and by ana
 elementary lysis, that the third fraction, 112 C / 0.5 mm, is the pro
 desired duit.  The yield is 35.6 g (57.6% of the yield
 theoretical). 



   2.  1- [ss- (2,4-dimethylphenyl) hexyl] imidazole: the
 imidazole derivative from alcohol by implementation of the
 method of example 1, parts 3 and 4. 



   Example 62: 1 [α-( 2,4-dimethoxyphenyl) hexyl] imidazole
 1.    242,4-dimethoxyphenyl) hexan-1-ol: to a stirred mixture, to
   5 "C, 27.6 g (0.20 M) of m-dimethoxybenzene, 52.1 g (0.20 M) of
 anhydrous stannic chloride and 200 ml of methylene chloride in
 which we constantly pass a stream of nitrogen, we add
 dropwise 20.0 g (0.20 M) of 1,2-epoxyhexane in 50 ml of
 methylene chloride.  The reaction mixture, which heats up because
 that the reaction is exothermic, is maintained at 3 C by adjusting
 the pace of addition. 

  After the addition is completely finished,
 the reaction mixture is stirred at 5 "C for 30 min, and then
 pour it into ice-cold concentrated hydrochloric acid.  Layers
 separate; the aqueous layer is extracted using chloride
 methylene.  The organic layers are combined, washed with
 water, then with a 5% aqueous solution of sodium bicarbonate, and finally with water.  The last wash water is neutral to pH paper.  The solvent is removed (methylene chloride) on a rotary evaporator at 40 ° C (bath temperature).  A residue is thus obtained which is subjected to fractional distillation under vacuum. 

  It is proved, by nuclear magnetic resonance and infrared spectrography, that the third fraction, 140-142 "C / 0.2 mm, is the desired product.  25.32 g are obtained (55% of the theoretical yield). 



   2.    1- [ag2,4-dimethoxyphenyl) hexyl] imidazole: the methanesulfonate is formed from the above alcohol by implementation
 of the method of example 1, part 3.  However, during the reaction
 methanesulfonate with imidazole by the method of example 1 part 4, a transposition takes place and the a-substituted product is obtained which is identified by infrared and by nuclear magnetic resonance. 



  Example 66:
 1 - [a- (2,4-dichlorobenzyl) pentyl] imidazole
 1.    α-( 2,4-dichlorobenzyl) pentan-1-ol: 7.5 g (384 mM) turn
 magnesium nures in 150 ml of ether, a portion of
 10.0 g (51 mM) of a, 2,4-trichlorotoluene and a few iodine crystals. 



  When the color of the iodine has dissipated, the reaction mixture is heated to reflux, and 58.0 g (297 mM) of additional alpha, 2,4-trichlorotoluene in 50 g of it are added thereto. ether at a rate such that reflux is maintained.  When the addition is completely complete, the reaction mixture is stirred at reflux for 2 h, then cooled. 



  To this reaction mixture is added 17.0 g (197 mM) of valeraldehyde, and the reaction mixture is again heated at reflux for 2 h.  The mixture is cooled, poured into ice-cold dilute hydrochloric acid, then the organic phase is separated.  The aqueous solution is extracted with ether and the extract is combined with the organic phase.  After washing with water, the organic solution is dried over anhydrous magnesium sulphate, the solvent is removed by distillation, and 57.2 g of crude product are thus obtained.  Distillation provides 11.3 g (23%) of the product.  Its degree of purity is determined by chromatography. 



   2.  1- (2,4-Dichlorobenzyl) pentyl methanesulfonate: the methanesulfonate is prepared by using the method of Example 1, part 3, it is identified by infrared, and its degree of purity is determined by chromatography. 



   3.    1- [a- (2,4-dichlorobenzyl) pentyl] imidazole: the imidazole derivative is prepared by using the method of the example
 1, part 4, it is identified by infrared, nuclear magnetic resonance and elementary analysis, and its degree of purity (greater than 95%) is determined by chromatography. 



  Example 67: 1 [(32,4-dichlornbenzyl) hexyl] imidazole
 1.  Ethyl malonate and a "(2,4-dichlorobenzyl): to 4.6 g (95 mM) of 50% NaH in 250 ml of anhydrous THF, 16.0 g (100 mM) are added with stirring ) ethyl malonate; the reaction suspension is stirred for 1 h, then heated to reflux for 3 h.  The reaction mixture is cooled, and added to it
 17.5 g (90 mM) x, 2,4-trichlorotoluene.     The resulting reaction suspension is heated at reflux for 16 h.  The reaction mixture is then cooled, and the THF is distilled off.  The concentrate is stirred with water, and the ester type product is extracted with ether. 

  The ethereal solution is washed with water, dried over anhydrous magnesium sulphate, then concentrated and the crude product is thus obtained.  The residue is heated to 110 ° C. under a pressure of 0.1 mm, the excess ethyl malonate is distilled off, which leaves 27.1 g (94%) of the product.  It is found, by chromatography, that its degree of purity is greater than 95%. 



   2.  Ethyl malonate and a-butyl-a- (2,4-dichlorobenzyl): to 6.7 g (140 mM) of 50% NaH in 500 ml of anhydrous THF, 44.2 g are added at reflux (139 mM) ethyl malonate and a- (2,4-dichlorobenzyl) prepared as described above, and the resulting suspension was stirred at reflux temperature for 16 h. 



  The reaction mixture is cooled, and 26.6 g (140 mM) of 1-iodobutane are added thereto.  This mixture is heated to reflux while stirring for 6 h. 



   The solvent is distilled off, and the concentrate is stirred with 500 ml of water.  A product is separated which is extracted using ether; the ether extract is washed twice with 100 ml of water.  After drying over anhydrous magnesium sulfate, the ether is distilled off and 60 g (more than 100%) of crude product are collected. 



  A degree of purity of 95% is determined by chromatography. 



   3.  Ag2,4-dichlorobenzyl) hexanoic acid: to 45.0 g (400 mM) of 50% potassium hydroxide, 52.4 g (140 mM) of ethyl malonate and a-butyl-a- ( 2,4-dichiorobenzyl), and the mixture is stirred at reflux for 16 h.  The reaction mixture is cooled, and washed twice with 75 ml of benzene.  The aqueous solution is treated with concentrated hydrochloric acid, and the malonic acid derivative is separated by sedimentation.  The oil is separated, and the aqueous solution is extracted using xylene.  The extract is combined with the oil, dried over anhydrous magnesium sulfate and heated to reflux.  

  After 2 h, the xylene is distilled off until the temperature of the flask reaches 180 C.  The reaction mixture is cooled, which gives 46.0 g of crude product
 4.  2- (2,4-dichlorobenzyl) hexan-1-ol: to 9.4 g of lithium aluminum hydride in 600 ml of THF, 46.0 is added slowly, at a temperature below 10 ° C. g of crude 42,4-dichlorobenzyl) hexanoic acid.  The reaction mixture is stirred, and allowed to warm slowly to room temperature. 



  After 2 h, the suspension is heated to reflux and kept there for 16 h.  At the end of this time, the reaction mixture is cooled and it is carefully poured into ice water to decompose the excess LiAlH4.  The mixture is then acidified by treating it with concentrated hydrochloric acid.  The ethereal solution is separated, and the aqueous phase is extracted three times with 200 ml of ether.  The extracts and the ethereal solution are combined and washed with 100 ml of a dilute aqueous solution of sodium bicarbonate, then with 100 ml of water.  The solution is dried over anhydrous magnesium sulfate, then the ether is distilled off and 35.9 g of the crude product (alcohol) are thus collected.  Distillation (86.8 C / 0.15 mm) gives 34.2 g (93%) of said pure alcohol. 

  This substance is identified by infrared, and its degree of purity is determined by chromatography. 



   5.    22,4dichlorobenzyhexyl methanesulfonate: the methanesulfonate is prepared by using the method described in example 1, part 3; the product is identified by infrared, and its degree of purity is determined by chromatography. 



   6.    1- [ss- (2,4-dichlorobenzyl) hexyl] imidazole: the imidazole derivative is prepared by using the method described in example 1, part 4; the product is identified by infrared, nuclear magnetic resonance and elementary analysis, and its degree of purity (found greater than 95%) is determined by chromatography. 



  Example 68: 1 - [α-( 2,4-dichlorophenyl) heptyl] imidazole
 1.  2- (2,4-Dichlorophenyl) hexyl cyanide: to a suspension of 11.3 g (230 mM) of sodium cyanide in 100 ml of dry dimethylformamide (DMF), a solution of 50 g is added dropwise 154 mM) of 2- (2,4-dichlorophenyl) hexyl methanesulfonate in 50 ml of DMF.  The reaction mixture is stirred at 70 ° C overnight.  It is then poured into 500 ml of water, then it is extracted with ether.  The ethereal extracts are combined, then washed with water, then with a saturated sodium chloride solution, and finally they are dried over magnesium sulfate. 

  The solvent is evaporated off under reduced pressure, and 37 g of crude product are thus obtained which are further purified by vacuum distillation (107.5 110 "C / 0.05 mm), which gives 33.9 g (86 %) of the desired product. 



   2.  2- (2A-dichlorophenyI) heptanoic acid: a mixture of 15 g (59.6 mM) of 2- (2,4-dichlorophenyI) hexyl cyanide and 100 ml of sulfuric acid is heated to 110 ° C. overnight. 50%. 



  The reaction mixture is then cooled, then diluted with 500 ml of water.  This aqueous portion is extracted with ether, the ethereal extracts are combined and dried over magnesium sulfate. 



  The solvent is removed under reduced pressure, which gives 15.02 g (93.7%) of a white solid, P. F.    65-68 C.    



   3.  3- (2,4-dichlorophenyl) heptan-1-ol: to a suspension of 2.07 g (54.5 mM) of lithium aluminum hydride in 100 ml of ether, dropwise added a solution of 15 g (54 mM) of 242,4-dichlorophenyl) heptanoic acid in 50 ml of ether.  The resulting mixture is stirred at room temperature for 3 h. 



  The excess lithium aluminum hydride is carefully decomposed with 100 ml of a saturated ammonium chloride solution, then 100 ml of a dilute sulfuric acid solution. 



  The ethereal layer is separated from the aqueous layer, and the aqueous layer is extracted again with ether.  The ethereal layers are combined and washed with 10% sulfuric acid, with water, with saturated sodium bicarbonate solution, with saturated sodium chloride solution, then dried over sodium sulfate. magnesium.  The solvent is evaporated off under reduced pressure, and 12 g of an oil are thus obtained which is further purified by vacuum distillation (120-125 C / 0.1 mm), which gives 10.2 g (72% ) of the desired product. 



   4.  3- (2,4-dichlorophenyl) heptyl methanesulfonate: at 10.2 g (39 mM) of 3 {2,4-dichlorophenyl) heptan-1-ol and 4.8 g (42 mM) of methanesulfonyl chloride in 100 ml of benzene at 10 ° C., 4.4 g (43 mM) of triethylamine are added slowly.  When the addition is completely complete, the reaction mixture is stirred and allowed to warm to room temperature over a period of 30 min.  The reaction suspension is then heated at reflux for 30 min, then cooled and poured into water.  The organic solution is washed with dilute hydrochloric acid, then with water and finally with a dilute solution of sodium bicarbonate. 

  After drying over anhydrous magnesium sulfate, the benzene is removed by distillation, which gives 10.6 g of product of the crude sulfonate type. 



   5.    1 - [α-( 2,4-dichlorophenyl) heptyl] imidazole: to 10.6 g (160 mM) of imidazole at 95 ° C., 10.9 g (42 mM) of 342 'methanesulfonate are added, 4 -dichlorophenyl) crude heptyl.  The materials are stirred at 95 ° C for 16 h, then cooled and poured into 500 ml of water.  After stirring for 1 h, the organic layer is separated and the aqueous layer is extracted with ether.  The ether extract is combined with the organic phase and, after washing with water, the solution is dried and concentrated, which gives 10.6 g of the crude product. 



  Example 69:
 1- [ss- (2,4-dichlorophenyl) phenethyl] imidazole
 1.    α-( 2,4-dichlorophenyl) phenylacetaldehyde: to 47.1 g (188 mM) of 2,4-dichlorobenzophenone and 36.2 g (289 mM) of ethyl chloroacetate, 14.9 g ( 310 mM) 50% sodium hydride at 15 C.  The reaction mixture is stirred and allowed to warm slowly to room temperature overnight.  The reaction mixture is added to ice water, and acidified with dilute hydrochloric acid.  The organic material is extracted with three 200 ml portions of benzene.  The extracts are combined, washed twice with 100 ml of water and dried over anhydrous magnesium sulfate. 

  Benzene was distilled off, and the crude product was added to 35.3 g (530 mM) 85% potassium hydroxide in 350 ml of water.  The mixture is heated to reflux for 20 h, cooled and washed twice with 200 ml of benzene.  The aqueous solution is acidified, and the organic acid separates as an oil.  This oil is collected and the aqueous solution is extracted twice with 200 ml of ether.  The extracts are combined with the oil, dried over anhydrous magnesium sulfate and concentrated, which gives 30.7 g of the hydroxy acid.  This residue is heated for 3 h to decompose it into the product of the crude aldehyde type, from which 24.3 g are thus collected.  Distillation (128-137 C / 0.05 mm) gives 16.3 g (33%) of the aldehyde. 



   2.  ss- (2,4-dichlorophenyl) phenethanol: to 2.4 g (61.5 mM) of LiAIH4 in 140 ml of anhydrous THF, 16.3 g (61.5 mM) are added dropwise at 0 ° C ) α-( 2,4-dichlorophenyl) phenylacetaldehyde in 60 ml of anhydrous THF.  When the addition is completely complete, the reaction mixture is stirred for 2 hours at 0 ° C., then for 16 hours at room temperature.  The reaction mixture is then heated to reflux temperature for 2 h, then cooled and poured into ice water.  The mixture is acidified with concentrated hydrochloric acid, and the organic material is extracted twice using 200 ml portions of ether. 

 

  The extracts are combined, dried over anhydrous magnesium sulfate, concentrated and 15.5 g of crude product are thus obtained. 



  Distillation (125-39 "C / 0.025 mm) gives 10.6 g (65%) of the product of the purified alcohol type.  This substance is identified by infrared, and its degree of purity is determined by chromatography. 



   3.  B- (2,4-dichlorophenyl) phenethyl methanesulfonate: methanesulfonate is prepared by using the method described in Example 1, part 3; the product is identified by infrared, and its degree of purity is determined by chromatography. 



   4.    1 [P2,4dichlorophenyl) phenethyi] imidazole: the imidazole derivative is prepared by using the method described in
Example 1, part 4; the product is recrystallized from acetone, which gives 2.6 g (32%) of the salt (hydrochloride),
P. F.    197-8 C.    



  Example 70:
 1 -CE- (2,4-dichlorophenyl) hexyl] imidazole
 1.  5- (2,4-dichlorophenyl) hexan-1-ol: a suspension of 735 g (5.0 M) of m-dichlorobenzene and 162 g (1.1 M) of chloride
 anhydrous aluminum is cooled to 10 "C using a bath
 of water and ice, and added dropwise to 1100 g (1.0 M)
 1,2-epoxyhexane.  The reaction temperature is maintained at
 below 15 C.  The reaction mixture is allowed to warm to room temperature and continues to stir for
 a night.  The reaction mixture is then poured, with stirring, into a
 41 flask containing ice and 50 ml of hydrochloric acid
 concentrated.  The aqueous layer is separated from the organic layer, and
 the aqueous layer is extracted three times with 150 ml of ether. 

  We reunite
 the ethereal extracts, washed twice with 50 ml of water, and washed
 dry over magnesium sulfate.  The solvent is evaporated, and a
 vacuum distillation (160-172 C / 0.1 mm) yields 114 g (46%) of
 product. 



   2.    1 - [# - (2,4-dichlorophenyl) hexyl] imidazole: we convert
 the primary alcohol into the sulfonate and the imidazole derivative into
 operating in the usual way. 



   Example 71: I - [a-methyl-42,4-dichlorophenyl) hexyl] imidazole
 1.  2,4-dichlorovalerophenone: 48.0 g (398 mM) chloride
 valeryl in 100.0 g (680 mM) of m-dichlorobenzene,
 portions, at a temperature below 5 C, 66.7 g (500 mM) of
 aluminum chloride.  When the addition is completely finished,
 the reaction mixture is stirred and allowed to slowly warm to room temperature for 2 h.  Then we heat it
 at reflux for 3 h, then stirred at room temperature
 for 16 h.  The reaction mixture is poured into ice water,
 and acidified with hydrochloric acid.  An oil is formed which
 separates, and the aqueous layer is extracted twice with 200 ml
 ether. 

  The oil and the ethereal extracts are combined, the solution is washed
 with water, it is dried and concentrated, which gives 122.2 g of
 gross product.  Distillation (89-93 C / 0.05 mm) gives 55.2 g
 (60%) of the product. 



   2.    α-( 2,4-dichlorophenyl) hexanal: 50.0 g (216 mM) 2,4-di
 chlorovalerophenone in 42.4 g (346 mM) of chloroacetate
 ethyl alcohol at 0 ° C., 8.7 g (363 mM) of hydride are added in portions
 sodium over a 4 hour period.  When the bill is com
 completely finished, the reaction mixture is stirred and left
 slowly warm up to room temperature for
 2 hrs.  The reaction mixture is then poured into ice water, and
 acidified with hydrochloric acid.  We extract the organ material
 stiff with ether, then dry the extract and concentrate it, which
 gives 89.2 g of the crude glycidic ester. 

  The residue is treated with 40.0 g
 (607mM) 85% potassium hydroxide in 400 ml of water, and
 heat the mixture for 2 hours on a steam bath.  We wash
 the alkaline solution with benzene, then acidified with acid
 hydrochloric.  An oil is formed which is extracted using ether,
 then the ethereal solution is dried and concentrated.  We dissolve the
 residue in xylene, the mixture is refluxed for 6 h, during the
 which it releases from carbon dioxide.  The solution is rectified until dry, which gives 32.4 g of the crude aldehyde A distillation
 (112-7 / 0.2 mm) gives 16.6 g (31%) of the product. 



   3.  3- (2,4-dichlorophenyl) heptan-2-ol: 14.3 g (88 mM) iodide
 methylmagnesium in 75 ml of ether, slowly added to a
 temperature below 10 "C, 59 mM a- (2,4-dichlorophenylf
 hexanal.  When the addition is completely finished, the reaction mixture is stirred for 1 h, then it is heated to reflux for 2 h.  The reaction mixture is cooled and poured into
 some water.  The mixture is acidified with hydrochloric acid; an oil is separated which is extracted using ether.  The ethereal solution is dried and concentrated, giving 11.7 g (76%) of the crude product. 



   4.    3- (2,4-DichlorophenyI) hept-2-yl methanesulfonate: methanesulfonate is prepared by using the method described in Example 1, part 3; the product is identified by infrared and its degree of purity is determined by chromatography. 



   5.    1- [a-methyl- (2,4-dichlorophenylhexyl] imidazole: the imidazole derivative is prepared by carrying out the procedure described in example 1, part 4; the product is identified by infrared, and it is determined its degree of purity by chromatography.  It thus appears that it contains approximately equal proportions of the isomers. 



  Example 72:
 1-CB-butyl hydrochloride- B- (2,4-dichlorophenyI) hexy-
 imidazole
 1.  Ethyl hexanoate α -butyl- α-( 2,4-dichlorophenyl): to 4.3 g (90 mM) of sodium hydride at 50% in 200 ml of anhydrous THF, 23.6 are added g (81.6 mM) of ethyl hexanoate and a- (2,4-dichlorophenyl), and the reaction mixture is heated at reflux for 72 h.  The reaction mixture is then stirred at room temperature for 72 h.  At the end of this time, 16.6 g (90 mM) of iodobutane are added, and the reaction mixture is heated at reflux for 24 h.  The reaction mixture is then cooled and poured into ice water, and the oil which forms is separated. 

  The aqueous phase is extracted with ether, and the extract is combined with the oil.     The ethereal solution is dried and concentrated, giving 14.2 g of crude product.  Distillation (150-70 C / 0.25 mm) gives 13.3 g of the desired ester. 



   2.  2-butyl-2- (2,4-dichlorophenyl) hexan-1-ol: the alcohol is formed using the method described in Example 1, part 2; 4.8 g of the pure product which is distilled at 133-8 / 0.05 mm are collected and identified by nuclear magnetic resonance. 



   3.  Reaction with imidazole: the imidazole derivative is formed by passing through methanesulfonate according to the methods described in example 1, parts 3 and 4.  1.5 g (28%) of final product are thus collected, P. F.    103-5 "C, recrystallized from acetone / ether and identified by nuclear magnetic resonance and by elemental analysis. 



  Example 73:
 1- [ss, ss-bis- (p-chlorophenyl) ethyl] imidazole
 1.  2,2-bis- (p-chlorophenyl) ethanol: to 15.1 g (397 mM) of lithium aluminum hydride in 750 ml of anhydrous THF at a temperature below 5 ° C., is added in portions, over a period of 2.95.0 g (338 mM) bisQp-chlorophenylS acetic acid.  When the addition is completely finished, the reaction mixture is stirred at 5 ° C. for 4 h, then it is allowed to warm up to room temperature overnight.  The reaction mixture is poured slowly into ice water, which gives off hydrogen.  The mixture is acidified with hydrochloric acid, and the organic phase which forms is separated. 

  The aqueous phase is extracted twice with 200 ml of ether and the extracts are combined with the organic phase.  The ethereal solution is dried and concentrated, which gives 74.7 g of crude product. This residue is distilled (157-162 C / 0.05 mm), which gives 35.3 g (39%) of the desired product. . 

 

   3.  Formation of the imidazole derivative: the imidazole derivative (P. F.    80-2 C) in the ordinary manner. 



  Example 74:
 1- [ss- (o and p-chlorophenyl) -p-chlorophenethyl] imidazole
 1.  2- (o and p-chlorophenyl) -chlorophenethyl chloride: to a mixture of 12.5 ml of 30% oleum in 25 ml of sulfuric acid, dropwise added at a temperature below 5 ° C., 11.6 g (0.76 M) of chloroacetaldehyde diethyl acetal in 34.0 g (0.30 M) of chlorobenzene.  When the addition is completely complete, the reaction mixture is stirred for 1 h, and allowed to warm to room temperature.  The reaction mixture is poured into ice water, and the organic phase is extracted twice with 200 ml of ether.  The extracts are dried and concentrated, giving 17.3 g of the crude yellow-orange product. 

  This substance is distilled to give 9.8 g (165-8 C / 0.4 mm) of the isomeric product. 



   2.  Reaction with imidazole: to 75 ml of methanol, 1.05 g (45.8 mM) of sodium are added to form a solution.  To this solution, 3.1 g (45.8 mM) of imidazole is then added, and the reaction mixture is evaporated to dryness.  50 ml of N, N-dimethylformamide are added to the wet solid residue.  The resulting solution is heated to 130 ° C., and the remaining methanol is removed by distillation. 



  To this solution in DMF, 8.7 g (30.5 mM) of 2- (o and p-chlorophenyl) -p-chlorophenethyl chloride are added, and the reaction mixture is heated to 130 ° C. for 48 h .  The reaction mixture is cooled, poured into ice water, and the organic material is extracted with stiff ether.     The ether extract is cooled and treated with hydrochloric gas.  The salt which forms as an oil is separated and then treated with a solution of sodium bicarbonate.  The resulting mixture is extracted with ether, then the ethereal solution is dried and concentrated, to give 0.6 g of the product. 



  Example 75:
 1- [ss, ss-tetramethylene-ss- (2,4-dichlorophenyl) ethyl nitrate]
 imidazolium
 1.  A, ot-tetramethylene-2,4-dichlorobenzyl cyanide: 200 ml of a 25% sodium hydroxide solution and 4 g of tetraethylammonium bromide are placed in a 500 ml flask with three necks.  To this suspension, a solution of 33.5 g (0.2 M) of 2,4-dichlorobenzyl cyanide and 43 g (0.2 M) of 1,4-dibromobutane in 200 ml of chloride is added dropwise. of methylene under a nitrogen atmosphere.  When the addition is complete, the reaction mixture is heated to reflux for 1 h 2 h. It is then poured into water, then the layers are separated.  The aqueous layer is extracted with 100 ml of methylene chloride. 

  The organic extracts are combined, washed with water, with a saturated sodium chloride solution, then dried over magnesium sulfate.  The solvent is evaporated, which gives a pale yellow oil.  Vacuum distillation (13s140 C / 0.2 mm) gives 30.4 g (63%) of pure product, which is identified by nuclear magnetic resonance. 



   2.    Acidex, a-tetramethylene-2,4-dichlorophenylacetic: a mixture of 14 g (60 mM) of α cyanide, α-2,4-dichlorobenzyl cyanide is heated for 3 days at reflux, 160 ml of a 40% solution of potassium hydroxide, and 120 ml of diethylene glycol.  The reaction mixture is then poured into water and then extracted with ether.  The aqueous layer is then acidified with hydrochloric acid, then extracted with ether.  The ethereal extracts from the acid solution are combined and washed with water, with saturated sodium chloride solution, and then dried over magnesium sulfate. 

  The solvent is evaporated, which gives 12.4 g of crude acid which is recrystallized from hexane / benzene; 8 g of pure acid are thus collected, P. F.  136-138 C. 



   3.  2,2-Tetramethylene-2- (2,4-dichlorophenyl) ethyl alcohol: to a suspension of 3 g (80 mM) of lithium aluminum hydride in 300 ml of anhydrous ether, dropwise added 13 g (50 mM) of α, α -tetramethylene-2,4-dichlorophenylacetic acid in 50 ml of ether under a nitrogen atmosphere.  The reaction mixture is then heated at reflux for 1 h.  The excess LiAIH4 is carefully decomposed by the dropwise addition of 10% hydrochloric acid to the reaction mixture.  It separates two layers; the aqueous layer is extracted with ether. 



  The ethereal extracts are combined, washed with water, and dried over magnesium sulfate.  The solvent is evaporated off, which gives 9.8 g of the desired alcohol, which is identified by nuclear magnetic resonance. 



   4.  2,2-tetramethylene-2- (2,4-di-) methanesulfonate
   chlorophenyl) ethyl: to a mixture of 9.8 g (40 mM) of alcohol
   2,2-tetramethylene-2 (2,4-dichlorophenyl) ethyl and 5 g
 (40 mM) of methanesulfonyl chloride in 30 ml of benzene,
 5 g (50 mM) of triethylamine are added dropwise.  We shake it
 reaction mixture at room temperature overnight.  he
 a precipitate is formed which is filtered.  Wash the benzine solution
 fuck with water, then dilute hydrochloric acid, and wash it
 dry over magnesium sulfate.  The solvent is evaporated, and
 collects 12 g of the desired product, identified by nuclear magnetic resonance. 



   5.  1- [ss, ss-tetramethylene-ss- (2,4-dichlorophenyl) ethyl] irnidazole: a mixture of 12 g is heated for 24 hours
 (37 mM) of 2,2-tetrameffiylene-22,4di- methanesulfonate
 chlorophenyl) ethyl, 10 g (150 mM) imidazole, and 1 ml of dimethylformamide.  The reaction mixture is poured into water and then extracted with ether.  The ethereal extracts are combined, washed with water, then dried over magnesium sulfate.  We separate
 the drying agent by filtration, and to the ethereal solution is added dropwise concentrated nitric acid.  A white precipitate is formed which is collected by filtration and which is dried under vacuum. 

  This gives a total of 3.7 g of salt, P. F.       176-179 C, which is identified by nuclear magnetic resonance. 



  Example 101: I - [ss {2,4-dichlorophenyl) hexyl] 4-nitro-imidazole
 To 3.5 g (30.7 mM) of sodium hydroxide in 150 ml of methanol, 3.5 g (30.7 mM) of 4-nitro-imidazole are added, then the solution is heated and removed. methanol by distillation.  To the concentrate, 100 ml of DMF are added and the solution is heated to 120 ° C. to remove the rest of the methanol and water.  This gives a solution (in DMF) which is cooled to a temperature below 900 ° C., and 10.0 g (30.7 mM) of 2- (2,4-dichlorophenyl methanesulfonate) are added thereto. ) hexyl.  The reaction mixture is heated to 145 ° C for 2 h, then cooled and poured into water. 

  The organic material is extracted with ether and, after drying, the solvent is removed and 11.2 g of residue are thus collected.  This concentrate is triturated with hexane, then dissolved in 25 ml of methanol.  The methanolic solution is slowly poured into water, and a gummy solid is formed.  This solid is separated by filtration, dried and recrystallized from acetone / hexane, which gives 4.2 g (41%) of the desired product, P. F. 67-9 C.    



  Example 102:
 1- [ss- (2,4-dichlorophenyl) hexyl] -4,5-dichloro-imidazole
 To 100 ml of methanol, 1.7 g (73.5 mM) of sodium are added. 



  When the sodium is dissolved, 10 g (73.5 mM) of 4,5-dichloro-imidazole are added.  The mixture is stirred until a solution is formed, then the methanol is distilled off.  The wet residue is then added to 50 ml of DMF, and the solution is heated to 125 C to remove the remains of methanol and water.  The solution is cooled below 100 ° C. and 2.5 g (73.5 mM) of 2- (2,4-dichlorophenyl) hexyl methanesulfonate are added thereto.    



   The reaction mixture is warmed up to 130 C for 2 h, then
 we cool it.  The reaction mixture is poured into water and the organic material is extracted three times with 200 ml of benzene.  The extracts are combined, washed twice with 50 ml of water, dried over anhydrous magnesium sulphate, concentrated and 15.8 g of the crude product are thus obtained.  The residue is dissolved in ether, and treated with dry hydrochloric gas.  We separate the solu
 ethereal tion by decantation of the oil which forms, and this oil is triturated twice with 150 ml of ether.  The oil is then treated with
 10% sodium hydroxide, then the product is extracted twice at
 using 200 ml of ether.  

  The ethereal solution is dried and then con
 center, giving 12.6 g (47%) of the product as an oil.   



  Example 103:
 1- [ss- (2,4-dichlorophenyl) hexyl] -3-butylimidazolium iodide
 5.0 g (16.8 mM) of 1- [ss- (2,4-dichlorophenyl) hexyl] - imidazole is heated for 2 h on a steam bath with 3.1 g (16.8 mM) 1-iodobutane.  The reaction mixture is cooled and triturated three times with 50 ml of ether.  The oily residue is evaporated to dryness and 5.3 g (66%) of the product are collected in the form of an oil. 



  Example 104:
 1- [ss- (2,4-dichloro-5-nitrophenyl) hexyl] nitro-imidazole
 To 20.0 g (67 mM) of 1-CB- (2,4-dichlorophClnyl) hexylimidazole in 40 ml of sulfuric acid, 80 ml of nitric acid and 40 ml of sulfuric acid are slowly added.  The reaction mixture is heated for 14 h on a steam bath, then cooled and poured into water.  The acidic aqueous solution is separated by decantation from the oil which forms.  The residue is washed twice with 75 ml of water, then it is taken up in a mixture of acetone and benzene, dried and concentrated, which gives 14.9 g of the crude product.  To purify it, 3.0 g of this crude product are dissolved in hot methanol. 

  By cooling, the product separates by precipitation; it is collected by filtration and dried, which gives 1.6 g of the nitro-imidazole derivative. 



   Tables I and II show some of the compounds prepared by the procedures described in the previous examples. 



   Note that the above examples are not numbered according to the unbroken sequence of numbers.  The reason for this is that only the typical procedures have been described in detail. 



  On the other hand, the examples from 1 to 104 are repeated without interruption in Table I, where all the variants are specified in detail. 



  Table I
EMI16. 1

EMI16. 2


 <tb> Example <SEP> Z <SEP> (A), <SEP> Rl <SEP> Rl2 <SEP> (B) nt <SEP> (Xl) al <SEP> MY
 <tb> N "
 <tb> <SEP> 1 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 2 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> <SEP> 3 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C4Hon <SEP> H <SEP> CH2 <SEP> - <SEP> 2 / 2ZnCI2
 <tb> <SEP> 4 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> C2H204
 <tb> <SEP> 5 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP> V2CuBr2
 <tb> <SEP> 6 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> KCuS04
 <tb> <SEP> 7 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> t / 2CoCI2
 <tb> <SEP> 8 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP> I / 2NiS04
 <tb> <SEP> 9 <SEP> 2,4-Cl2C6H3 <SEP> -

    <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> t / 2FeCI2
 <tb> 10 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> ViCr (NO3) 3
 <tb> 11 <SEP> 2,6-C12C6H3 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> 12 <SEP> 2-CH3CsH4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 13 <SEP> 3-CH3C6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 14 <SEP> 4-CH3C6H4 <SEP> - <SEP> C4H9a <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> 15 <SEP> 4-CH3O-C6H4 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 16 <SEP> C6Hs <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 17 <SEP> 4-ClC6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> HC1
 <tb> 18 <SEP> 4-CICsH4 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 19 <SEP> 3-ClC6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2
 <tb> 20 <SEP> 2-CIC6H4 <SEP> - <SEP> C4Hon <SEP> H <SEP> CH2 <SEP> -

    <SEP> HCI
 <tb> 21 <SEP> 3,4-Cl2C6H3 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 22 <SEP> 2,4- (CH3) 2C6H3 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 23 <SEP> 3-CF3C6H4 <SEP> - <SEP> C4Hon <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 24 <SEP> 4-FC6H4 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 25 <SEP> 4-BrC6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> 26 <SEP> 4-CH3SC6H4 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP> HNO3
 <tb> 27 <SEP> 4-CH3SO2C6H4 <SEP> 27 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 28 <SEP> 4- (t-C4H9) C6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 29 <SEP> 4-N02C6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 30 <SEP> 4-NH2C6H4 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 31 <SEP> 2,4-Cl2-5-NO2C6H2 <SEP> - <SEP> C4H <SEP> H <SEP> CH2 <SEP> - <SEP>

   HCI
 <tb> 32 <SEP> 2.6- (CH3) 2C6H3 <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 33 <SEP> 3.5- (CH3) 2C6H3 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 34 <SEP> C6Hs-C6H5 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 35 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP>
Table I (continued)
EMI17.1

EMI17.2


 <tb> Example <SEP> Z1 <SEP> (A) n <SEP> Ri <SEP> R2 <SEP> (B) nt <SEP> (it) " <SEP> MY
 <tb> N "
 <tb> 36 <SEP> 3¯ <SEP> - <SEP> C4H9u <SEP> H <SEP> CH2 <SEP> - <SEP> 2HNOJ
 <tb> 37 <SEP> HERE <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP> C2H204
 <tb> 38 <SEP> g <SEP> - <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 39 <SEP> 1010) <SEP> - <SEP> C4H9u <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 40 <SEP> - <SEP> I <SEP> 7 <SEP> e <SEP> J <SEP> - <SEP> C4Hon <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 41 <SEP> - <SEP> <SEP> 7 <SEP> e <SEP> - <SEP>

   C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> 42 <SEP> fAF <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> 43 <SEP> SU <SEP> ON <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> <SEP> CF <SEP> OH
 <tb> 44 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> 45 <SEP> C.v. <SEP> e <SEP> ho <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> 46 <SEP> b, ¯ <SEP> 4 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> W <SEP> ¯ <SEP> C4Hsll <SEP> H <SEP> CH2 <SEP>
 <tb> 48 <SEP> i <SEP> - <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP>
 <tb> 49 <SEP> 2,4-C12C6H3 <SEP> - <SEP> -CH2CH = CH2 <SEP> H <SEP> CH2 <SEP> - <SEP> HNO3
 <tb> 50 <SEP> 2,4-CI2C6H3 <SEP> - <SEP> 4-ClC6H4CH2- <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 51 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> - (CH2) 2C6H4F-4 <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> 52 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C6H11 <SEP> H <SEP> CH2 <SEP> - <SEP> 2HtOHCI
 <tb> <SEP> oe
 <tb> 53 <SEP> 1134 <SEP> CHJ

    <SEP> H <SEP> CHr
 <tb> 53 <SEP> - <SEP> CH3 <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 54 <SEP> C <SEP> &commat; <SEP> - <SEP> CH3 <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> 55 <SEP>> <SEP> - <SEP> C2H5 <SEP> H <SEP> CH2 <SEP> - <SEP> HNO3
 <tb>
Table I (continued)
EMI18.1

EMI18.2


 <tb> Example <SEP> Z, <SEP> (A) n <SEP> R1 <SEP> R? <SEP> (B) 0 <SEP> (Xl) ax <SEP> MY
 <tb> N "
 <tb> <SEP> 56 <SEP> &commat;

  > <SEP> - <SEP> C2Hs <SEP> H <SEP> CH2 <SEP> - <SEP>
  <SEP> CH- / <SEP> C2H5 <SEP> H <SEP> CH2
 <tb> <SEP> 57 <SEP> CH <SEP> s <SEP> - <SEP> C2H5 <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 3
 <tb> <SEP> CH3
 <tb> <SEP> 58 <SEP> CN3 <SEP> - <SEP> C2H5 <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> OH
 <tb> <SEP> 3¯ <g <SEP> C6Hl3n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 60 <SEP> CH3 <SEP> i <SEP> - <SEP> CsH13n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 61 <SEP> CE-5 {+ Ctn <SEP> - <SEP> C6Hl3n <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> GC: -.
 <tb>



    <SEP> 62 <SEP> C¯ <SEP> C4 <SEP> CH2 <SEP> C4Hgn <SEP> H <SEP> - <SEP> - <SEP>
 <tb> <SEP> 63 <SEP> 2,4'6- (CH3) 3C6H2 <SEP> CH2 <SEP> C6H13n <SEP> H <SEP> - <SEP> - <SEP>
 <tb> <SEP> 64 <SEP> 2,4,6 (CH3) 3C6H2 <SEP> CH2 <SEP> C2H5 <SEP> H <SEP> - <SEP>
 <tb> <SEP> 65 <SEP> 2,4'6- (CH3) 3C6H2 <SEP> CH2 <SEP> C4H9n <SEP> H <SEP> - <SEP> - <SEP>
 <tb> <SEP> 66 <SEP> 2,4-C12C6H3 <SEP> CH2 <SEP> C4Hgn <SEP> H <SEP> - <SEP> - <SEP>
 <tb> <SEP> 67 <SEP> 2,4-C12C6H3 <SEP> CH2 <SEP> C4Hgn <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 68 <SEP> 2,4-C12C6H3 <SEP> C4Hsn <SEP> H <SEP> (CH2) 2 <SEP> - <SEP>
 <tb> <SEP> 69 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C6H5 <SEP> H <SEP> CH2 <SEP> - <SEP> HC1
 <tb> <SEP> 70 <SEP> 2,4-C12C6H3 <SEP> - <SEP> CH3 <SEP> H <SEP> (CH2) 4 <SEP> - <SEP>
 <tb> <SEP> 71 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C4Hgn <SEP> H <SEP> CHCH3 <SEP> - <SEP>
 <tb> <SEP> 72 <SEP> 2,4-C12C6H3

    <SEP> - <SEP> C4H9n <SEP> C4Hgn <SEP> CH2 <SEP> - <SEP> HCI
 <tb> <SEP> 73 <SEP> 4-ClC6H4 <SEP> - <SEP> 4-ClC6H4 <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 74 <SEP> 4-ClC6H4 <SEP> - <SEP> C <SEP> e <SEP> H <SEP> CH2 <SEP> - <SEP>
 <tb> <SEP> 75 <SEP> 2,4-C12C6H3 <SEP> - <SEP> -CH2CH2CH2CH2- <SEP> CH2 <SEP> - <SEP> HNO3
 <tb> <SEP> 76 <SEP> 4-CH3C6H4 <SEP> - <SEP> 4-CH3C6H4 <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> <SEP> 77 <SEP> 4-BrC6H4 <SEP> - <SEP> C4Hsn <SEP> H <SEP> CH2 <SEP> - <SEP> R
 <tb> <SEP> 78 <SEP> 4 <SEP> - <SEP> CICsH4 <SEP> - <SEP> 4-ClC6H4 <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> <SEP> 79 <SEP> 4-ClC6H4 <SEP> - <SEP> 2-Cl · H4 <SEP> H <SEP> CH2
 <tb> <SEP> 80 <SEP> 2,4-C12C6H3 <SEP> (CH2) 2 <SEP> C4H9n <SEP> H <SEP> CH2 <SEP> - <SEP> HCI
 <tb> <SEP> 81 <SEP> 2,4-C12C6H3 <SEP> - <SEP> H <SEP> H <SEP> CH2 <SEP> - <SEP> HNO3
 <tb> <SEP> 82 <SEP> 2,4-C12C6H3 <SEP> - <SEP>

   CH3 <SEP> H <SEP> CH2 <SEP> HCI
 <tb> <SEP> 83 <SEP> 2,4-C12C6H3 <SEP> - <SEP> CH3 <SEP> H <SEP> CH2 <SEP>
 <tb> <SEP> 84 <SEP> 2,4-Cl2C6H3 <SEP> - <SEP> C2H5 <SEP> H <SEP> CH2 <SEP>
 <tb> <SEP> 85 <SEP> Z4-C12C6H3 <SEP> - <SEP> C6Hl3n <SEP> H <SEP> CH2 <SEP>
 <tb> <SEP> 86 <SEP> 2,4-C12C6H3 <SEP> - <SEP> C8Hl7n <SEP> H <SEP> CH2 <SEP>
Table I (continued)
EMI19.1

Example ZI (A) n RIÚ RIê (B) n '(XI) aI MY
N 87 2,4-Cl2C6H3 ClOH2ln H CH2 - 88 2,4-Cl2C6H3 - -CH2CH (CH3) 2 H CH2 - 89 2,4-Cl2C6H3 - C6H5CH2- H CH2 - 90 2,4-Cl2C6H3 - C6H5 (CH2) 2- H CH2 - 91 2,4-Cl2C6H3 - C6H9 H CH2 - HCI 92 C6H5 - C6H5 H CH2 - HCl 93 4-Cl-C6H4 - C6H5 H CH2 - 94 2,4-Cl2C6H3 CH2 CH3 H - - 95 C6H5 CH2 C4H9n H - - 96 C6H5 CH2 CH3 H - - 97 C6H5 - CH3 CH3 CH2 - HCl 98 2 or 4-ClC6H4 - CH3 H (CH2) 2 - 99 4Cl-C6H4 - CH3 CH3 CH2 - HCl 100 2,4-C12C6H3 - <RTI

    ID = 19.3> C4Hsn H CH2 2-CH3 101 2,4-C12C6H3 - C4H9ll H CH2 4-NO2 H20 102 2,4-C12C6H3 - C4H9n H CH2 4,5-Cl2 103 2,4-Cl2C6H3 - C4H9n H CH2 3 -C4H9n HI 104 2,4-C12-5-NO2C6H2 - C4H9n H CH2 -NO2
 Table II
 Elementary analyzes (calc.)
Example N P.F. C C H Cl N O Other
 1 conc.

   60.64 6.16 24.01 9.16
 (60.62) (6.10) (23.86) (9.42)
 2 139-41 51.48 5.60 30.30 7.89
 (53.99) (5.74) (31.87) (8.40)
 3 57-63 48.75 4.94 29.70 6.88 7.58
 (49.31) (4.97) (29.11) (7.67) Zn = (8.95)
 4,126-8 54.22 5.33 19.20 7.56 14.16
 (52.73) (5.21) (18.31) (7.23) (16.53)
 5,219-21 38.00 3.92 16.26 5.87 13.00
 (44.06) (4.44) (17.34) (6.85) Cu = (7.77)
 6 61-4 52.35 5.38 21.08 7.51 5.49 4.70
 (47.79) (4.81) (18.81) (7.43) (8.49) Cu = (8.43)
 7 53-8 49.68 5.16 7.10 28.45 7.60
 (49.75) (5.01) (7.73) (29.37) Co = (8.14)
 8 107-113 45.75 4.87 18.96 6.91 10.54 5.23
 (48.05) (4.84) (15.23) (7.47) (8.53) Ni = (4.23)
 9 45-50 49.77 5.13 30.12 6.92 5.70
 (49.96) (5.03) (29.49) (7.77) Fe = (7.74)
 10 44-9 40.67 4.81 16.78 10.14 18.97 3.2
 (43.28) (4.36) (17.03) (11.78) (17.29) Cr = (6.24)
 11,154-6 53.63 5.74 31.79 8.26
 (53.99) (5.74) (31.87) (8.39)
 12 conc.

   77.93 9.21 - 11.32
 Table II (continued)
 Elementary analyzes (calc.) Example N 'P.F. "C C H Cl N O Other
 (79.29) (9.15) (11.56) 13 conc. 78.36 9.11 - 11.75
 (79.29) (9.15) - (11.56)
 14 126-8 68.65 8.47 12.21 9.75
 (68.92) (8.32) (12.71) (10.05)
 15 conc. 72.99 8.42 - 11.20 7.35
 (74.40) (8.58) - (10.84) (6.17) 16 conc. 77.36 8.70 - 11.87
 (78.90) (8.83) (12.27)
 17 72-3 56.82 6.26 22.24 8.91
 (60.21) (6.74) (23.70) (9.36)
 18 conc. 66.80 7.25 14.72 9.52
 (68.56) (7.29) (13.49) (10.66)
 19 conc. 66.08 7.19 12.78 10.25
 (68.56) (7.29) (13.49) (10.66) 20 103-6 56.76 6.32 22.09 8.23
 (60.21) (6.74) (23.70) (9.36) 21 conc. 60.25 6.27 24.91 8.30
 (60.61) (6.10) (23.85) (9.42) 22 conc. 78.06 9.46 - 10.83
 (79.64) (9.44) - (10.93) 23 conc. 63.31 6.34 - 10.84 18.62
 (64.85) (6.46) (9.45) F = (19.23) 24 conc.

   72-06 8.05 - 10.20 7.96
 (73.14) (7.77) (11.37) F = (7.71) 25 conc. 51.62 6.00 9.15 7.62 22.76
 (52.42) (5.87) (10.32) (8.15) Br = (23.25) 26 108-10 56.48 6.81 - 13.06 13.89 9.32
 (56.95) (6.87) (12.45) (14.22) S = (9.50) 27 conc. 62.06 7.48 - 8.57 10.86 9.62
 (62.71) (7.24) (9.14) (10.44) S = (10.47) 28 conc. 79.96 10.06 - 9.75
 (80.23) (9.92) (9.85) 29 conc. 65.40 7.19 - 15.42 12.53
 (65.91) (7.01) (15.37) (11.71) 30 conc. 73.64 8.92 - 16.84
 (74.03) (8.70) (17.27) 31 99-100 45.37 5.11 26.73 10.55) 11.72
 (45.41) (5.06) (26.81) (10.59) (12.09) 32 conc. 78.23 9.85 - 1,477
 (79.64) (9.44) (10.93) 33 conc. 78.97 9.79 - 10.54
 (79.64) (9.44) (10.93) 34 conc. 79.73 7.71 - 8.75
 (82.85) (7.95) (9.20) 35 conc.

   66.46 7.79 - 11.70 13.42
 (66.62) (7.74) (11.95) S = (13.68)
 36 103-5 47.38 6.06 - 19.96 26.24
 (47.32) (5.96) (19.71) (27.01)
 37 128-30 61.90 6.49 - 11.88 20.59
 (62.27) (6.60) (11.46) (21.83) 38 conc. 81.47 8.17 - 9.41
 (82.00) (7.95) (10.05) 39 conc. 78.95 7.80 - 9.25
 (82.00) (7.95) (10.05) 40 conc. 78.20 9.99 - 9.34
 (80.23) (9.92) (9.85)
 Table II (continued)
 Elementary analyzes (calc.) Example N0 P.F. "C C H Cl N O Other 41 conc. 74.50 9.51 - 9.67
 (79.94) (9.69) (10.36) 42 conc. 79.63 9.48 - 9.87
 (80.55) (9.01) (10.44) 43 conc. 76.36 9.50 - 10.32
 (79.64) (9.44) (10.93) 44 conc. 76.82 9.46 - 10.13
 (79.64) (9.44) (10.93) 45 conc. 77.50 9.30 - 10.46
 (78.28) (9.15) (11.56) 46 conc. 78.81 9.73 - 10.36
 (79.64) (9.44) (10.93) 47 conc. 78.30 8.49 - 9.19
 (82.00) (7.95) (10.05) 48 conc.

   81.12 8.21 - 9.68
 (82.85) (7.95) (9.20) 49 108-10 48.87 4.44 20.94 11.92 13.44
 (48.85) (4.39) (20.60) (12.21) (13.95) 50 conc. 58.58 4.54 28.86 7.44
 (59.12) (4.13) (29.09) (7.66) 51 152-3 57.04 4.58 26.60 7.17 4.50
 (57.08) (4.54) (26.61) (7.01) F = (4.75) 52 conc. 52.05 5.62 26.82 7.78
 (51.55) (5.85) (26.85) (7.07) 53 conc. 74.45 8.90 - 11.92
 (78.46) (8.46) (13.09) 54 conc. 76.82 8.23 - 13.75
 (77.96) (8.05) (13.99) 55 111-2 62.28 7.16 - 13.87
 (63.35) (6.98) (13.85) 56 conc. 78.48 9.18 - 11.56
 (78.90) (8.83) (12.27) 57 conc. 77.14 8.54 - 12.96
 (78.46) (8.46) (13.09) 58 conc. 77.71 8.94 - 11.74
 (78.90) (8.83) (12.27) 59 conc. 79.35 10.03 - 9.14
 (80.23) (9.92) (9.85) 60 conc. 79.47 9.70 - 9.27
 (79.94) (9.69) (10.36) 61 conc. 78.29 9.88 - 8.85
 (80.23) (9.92) (9.85) 62 conc. 70.60 8.10 - 9.90
 (70.80) (8.39) (9.72) 63 conc. 78.80 10.21 - 8.93
 (80.48) (10.13) (9.39) 64 conc.

   76.70 9.29 - 10.94
 (79.28) (9.15) (11.56) 65 conc. 79.75 9.96 - 10.20
 (79.94) (9.69) (10.36) 66 conc. 59.93 6.14 22.52 9.10
 (60.61) (6.10) (23.86) (9.43) 67 conc. 61.31 6.86 23.28 8.62
 (61.74) (6.48) (22.78) (9.00) 68 conc. 60.46 6.21 23.99 8.13
 (61.74) (6.48) (22.78) (9.00)
 Table II (continued)
 Elementary analyzes (calc.)
Example N "P.F." C C H Cl N O Other 69 197-8 58.82 4.38 28.44 8.04
 (57.73) (4.28) (30.07) (7.92) 70 conc. 60.39 6.46 23.50 8.94
 (60.62) (6.10) (23.86) (9.42) 71 conc. 61.33 6.42 23.10 8.34
 (61.74) (6.48) (22.78) (9.00) 72 103-5 54.93 6.54 25.44 6.70
 (58.55) (6.98) (27.29) (7.19) 73 80-2 64.59 4.44 21.81 8.65
 (64.37) (4.45) (22.35) (8.83) 74 conc.



  75 176-9 49.78 4.78 20.07 11.60 13.86
 (50.29) (4.78) (19.79) (11.79) (13.40) 76 195-7 69.42 6.81 11.15 8.75
 (72.94) (6.77) (11.33) (8.96) 77 conc. 57.40 6.01 - 8.25 28.58
 (58.64) (6.23) (9.12) Br = (26.01) 78 248-50 58.00 4.11 29.89 7.69
 (57.73) (4.28) (30.07) (7.92) 79 conc. 63.38 4.60 22.11 8.03
 (64.30) (4.41) (22.40) (8.85)
 80 137-8 56.50 6.54 28.83 7.97
 (56.44) (6.41) (29.40) (7.75)
 81 109-11 43.13 3.74 22.98 13.99
 (43.42) (3.61) (23.35) (13.81)
 82 163-6 49.20 4.54 36.07 9.60
 (49.42) (4.49) (36.47) (9.61)
 83 conc. 56.68 4.88 27.37 11.11
 (56.49) (4.74) (27.79) (10.98)
 84 conc. 56.95 5.33 26.26 10.02
 (58.01) (5.24) (26.34) (10.41)
 85 conc. 61.92 6.84 22.27 8.57
 (62.77) (6.82) (21.80) (8.61)
 86 conc. 63.16 7.23 19.54 7.17
 (64.59) (7.42) (20.07) (7.93) 87 conc. 65.32 8.05 18.35 5.84
 (66.00) (7.86) (18.65) (7.35) 88 conc.

   57.92 6.36 23.16 9.25
 (60.60) (6.07) (23.90) (9.43) 89 conc. 64.42 5.01 21.85 8.13
 (65.27) (4.87) (21.41) (8.46) 90 conc. 64.31 5.31 20.75 7.71
 (66.19) (5.25) (20.54) (8.11) 91 175-7 54.33 5.39 28.91 7.38
 (57.08) (5.35) (29.73) 7.83) 92 83-5 62.62 6.38 11.98 8.88
 (71.70) (6.02) (12.45) (8.94) 93 conc. 71.38 5.41 12.81 9.90
 (72.21) (5.35) (12.54) (9.91) 94 conc. 55.59 4.96 27.14 11.30
 (56.49) (4.74) (27.79) (10.98) 95 conc. 76.62 8.67 - 12.52
 (78.90) (8.83) (12.27) 96 conc. 76.58 7.57 - 15.08
 (77.38) (7.58) (15.04) 97,165 dec. 58.92 6.64 15.61 12.56
 Table il (continued)
 Elementary analyzes (calc.) Example N "P.F." C C H Cl N O Other
 (65.95) (7.24) (14.98) (11.83)
 98 conc. 65.70 6.74 15.09 11.58
 (66.52) (6.44) (15.10) (11.93)
 99 168-75 53.56 6.15 25.16 11.13
 (57.58) (5.95) (26.15) (10.33) 100 conc.

   58.73 6.70 23.79 7.86
 (61.74) (6.47) (22.78) (9.00) 101 67-9 50.65 4.90 19.39 11.63 13.54
 (50.05) (5.23) (19.70) (11.67) (13.33) 102 conc. 50.55 4.83 38.62 6.59
 (49.21) (4.40) (38.74) (7.65) 103 conc. 47.67 5.98 15.39 5.87 24.39
 (47.42) (5.66) (14.73) (5.82) I = (26.37) 104 - conc. 46.60 4.20 18.34 14.37 17.00
 (46.53) (4.17) (18.31) (14.47) (16.53)
 The metal salt complexes of the aralkyl imidazoles substituted in position 1 described above can be prepared by adding dropwise, with stirring, a stoichiometric proportion of a metal salt dissolved in a solvent suitable for a solution of the imidazole 1-aralcoylsubstituted dissolved in a similarly suitable solvent.

  The reaction mixture is briefly stirred, then the solvent is removed under reduced pressure to give the metal salt complex of the imidazole 1-aralkyl substituted in question. The identification and the degree of purity are determined by elementary analysis.



   The metal salt complexes can also be prepared by mixing a stoichiometric proportion or an excess of the metal salt with the imidazole 1-aralkyl substituted in the desired proportion of solvent containing the appropriate adjuvants just before application by spraying on plants. The adjuvants which can thus be incorporated in situ into this preparation can be detergents, dispersants, emulsifiers, wetting agents, spreading agents, sticky or adhesive agents, and the like commonly used for agricultural applications.



   Among the solvents which can be used to carry out these procedures are in particular any polar solvents such as, for example, water, methanol, ethanol, isopropanol or ethylene glycol, and any dipolar aprotic solvent such, for example, as dimethyl sulfoxide, acetonitrile , dimethylformamide, nitromethane or acetone.



   The metal salt cations which can be used for these procedures can be chosen from the group consisting of cations of the following metals: Ca, Mg, Mn, Cu, Ni, Zn, Fe, Co, Sn,
Cd, Hg, Cr, Pb and Ba, and the like.



   Any suitable anion, such as chloride, bromide, iodide, sulfate, bisulfate, phosphate, nitrate, perchlorate, carbonate, bicarbonate, hydrosulfide, hydroxide, acetate, can be used as the antagonist anion in the metal salt. oxalate, malate, citrate and the like.



   It has also been discovered that any metalliferous fungicide can also be used as a safety agent which can be used in place of metal salts. Typical metalliferous fungicides that can be used in these procedures are: a) dithiocarbamates and their derivatives such as ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), ethylenebisdithiocarbamate of manganese (maneb) and its coordination product with zinc ion ( mancozeb), zinc ethylenebisdithiocarbamate (zineb); b) copper-based fungicides such as cuprous oxide, copper naphthenate and Bordeaux mixture, and c) various fungicides such as phenylmercuric acetate, N-ethylmercuri-1,2,3,6 tetrahydro-3,6endométhanol-3 , 4,5,6,7,7-hexachlorophthalimide, phenylmercurimonoethanolammonium lactate, compounds containing nickel and calcium cyanamide.



   The above mentioned metal salt compounds and complexes are excellent as teletoxic protective / extirpating fungicides and have a high degree of activity against a wide variety of phytopathogenic fungi. Certain compounds are particularly effective in combating phytopathogenic fungi such as gray bean mold (Bothritis culera) on bean plants (Viciafaba); rice wilt (Piricularia oryzae) on rice plants; so-called late tomato rust (Phytophtora infestans) on tomato seedlings; powdery bean rust (Erysiphe polygoni) on bean plants; cross-linked staining of barley (Hel'inthosporium teres) on barley plants; downy rust of the vine (Plasmopora viticola) on young vine plants;

   rotting of lemon (Penicillium digitatum) on lemon fruit; apple scab (Venturia inaequalis) on young apple trees; powdery rust of wheat (Erysiphe graminis) on wheat or wheat plants; the black spot of wheat on wheat plants; wheat leaf rust (Puccinia recondita) on wheat plants; wheat stem rust (Puccinia graminis f. sp. tritici) on wheat plants; black rot or black rot of the vine (Guignardia bidwellii) on young vine plants; powdery cucumber rust (Erysiphe cichoracerum) on cucumber plants; and the organisms responsible for the production of aflatoxin (Aspergillusflavus).



   The extirpating fungicidal properties of the compounds in question are unique because they kill phytopathogenic fungi such as Helmintosporium teres in infected plant tissue, a property not found in common fungicides used to fight diseases caused by
Helminthosporium spp. The teletoxic properties possessed by the compounds in question are also unique and result in their ability to move both acropetally and basipetally in plant tissues.



   In free base form, these compounds can be used to destroy Helminthosporium oryzae supported on seeds, a property which other fungicides do not have, except organic mercury compounds.



   The compounds in question in the form of a free base exhibit growth-regulating activity on both monocotyledonous and dicotyledonous plants, the most pronounced effect being a retardation of the plant's growth. In some cases, particularly on dicotyledonous plants, some of these growth-regulating properties can be considered unfavorable. In such an eventuality, the responses of the plant to the effects of growth regulation and phytotoxicity can be suppressed by complexation of the imidazone compounds in question with the aid of metal salts chosen from the groups of the periodic classification of the elements already listed. above with regard to the preparation of said complexes included in the scope of the invention.



   For the evaluation of the compounds in question, it is necessary to carry out a preliminary fungicidal evaluation using the compounds at a concentration of 300 ppm and to spray the compositions on the plants until runoff in a vehicle volume corresponding to approximately 1400 I / ha.



   The general procedure is to take potted plants, which are in the proper growth state to make them susceptible to fungal disease; spraying is carried out on these potted plants which move on a conveyor belt, then left to dry. The appropriate plants are inoculated with the fungal spores, and incubated until the disease develops, and the degree of destruction of the phytopathogenic fungus is noted or estimated.

  The degree of disease control effectiveness, in percentage, is expressed by the following rating system:
 A = 97 to 100% control efficiency
 B control efficiency from 90 to 96%
 C = control efficiency from 70 to 89%
   D = control efficiency from 50 to 69%
 E = inactive: destruction of fungi 50%
 untreated plant disease
 Degree of destruction = disease of treated plants
 of disease% - disease of untreated plants x100
 The phytopathogenic fungi (or fungal organisms) used
 for the evaluation of the fungicidal activity of compounds and salts com
 taken within the scope of the invention are specified below, under the
 form of a code:

  :
 BH = cross-linked stain of barley (Helminthosporium teres)
 BOT = gray bean mold (Bothritis cinerea)
 BPM = powdery bean rust (Erysiphe polygoni)
 GDM = downy rust of the vine (Plasmopora viticola)
 TLB = late tomato rust (Phytophtora infestans)
 RB = rice wilt (Piricularia oryzae)
 WSR = wheat stem rust (Puccinia graminis f.sp. tritici)
 WLR = wheat leaf rust (Puccinia recondita)
 Table VI presents the results of the application of some
 some of the compounds and salts included in the scope of the invention, to a
 concentration of 300 ppm; Effectiveness is assessed against
   species of fungi specified above.



   Table T1
 Efficiency level (300 ppm)
Example BH BOT BPM GDM TLB RB WSR WLR
NOT
 1 A B A B E B - A
 2 A B A A B A - A
 3 A A A A B B - A
 4 E B A A A B - A
 5 A C A A B E - A
 6 A A A B B E - A
 7 A A A A A A - A
 Table VI (continued)
Example BH BOT BPM GDM TLB RB WSR WLR
NOT
 8 A A A A B B - A
 9 A A A A A A - A
 10 A A A A B A - A 11 E E A B B B - A
 12 A E A E B A - A
 13 E E A - E E - E
 14 A E A B A - - E
 15 A E A B E B - C
 16 A E E E C A - C
 17 A E A B A E - B
 18 A E A A A E - A
 19 E E A B B B - A
 20 A E A B A E - A
 21 A B A B B B - A 22 A E A A A B - A 23 E E E E E - E -
 24 A C A C E - C
 25 A C A E E - E -
 26 E C A E E - E -
 27 - E E E - - E <RTI

    ID = 24.17> -
 28 - E A E B - B -
 29 A C A C E - C 30 E E B C E A A -
 31 E C A E E - E
 32 B A A E E - C -
 33 E C A C B - E -
 34 E C A C E - B -
 35 A E A C E - E -
 36 E E A E E - E -
 37 38 A E A B A - B
 39 40 A E A E E - E -
 41 E C A E - - E 42 E E A C A - C
 43 E C A C E - E
 44 E E A B A - E -
 45 E E A E E A E - 46 A E A A E - C -
 47 A C E E E - C -
 48 A C A A E A A - 49 E B E C E - B -
 50 A B A B E - A -
 51 B A A B B - B
 52 A A A B E A A - 53 E E A E E E C - 54 E E A E E - E
 55 E E A E E - E
 56 <RTI

    ID = 24.31> A E A E E - E -
 57 E C A E E - E -
 58 A A E E E C E -
 59 A E A E E B B - 60 E C A E E B E - 61 E C A E E - E - 62 A C A E C - C -
 63 E B E C - - C 64 A E A E E - C - 65 A E A E A B E -
 66 B C A A A A C 67 A D A A B A - A
 68 A E B A B E - C 69 A A A B A A - A
 Table 1¯1 (continued)
Example BH BOT BPM GDM TLB RB WSR WLR N "
 70 A E E B B B - E
 71 A E A A B A - A
 72 E B A E E B - A
 73 A B B E B B - A
 74 A A A A A E - A
 75 A A A A A A - B
 76 E E A B B B - E
 77 E E A C E - E -
 78 A A A E B B - A
 79 E B A B - B - A
 80 A E A B C B - A
 81 E E A E E E - E
 82 A C A A C E - E
 83 A C A B B E -

   B
 84 A E A E E E - B
 85 E C A E E A - A
 86 A C A E E B - A
 87 A C E E E B - A
 88 E E A E E B - A
 89 E C A B B B - A
 90 E B A B B B - A
 91 A B A B B B - A
 92 E E A E B B - E
 93 A E A E B B - A
 94 A E A E E - - A
 95 E E A E E - - A
 96 E E E E E E - E
 97 E E E E E B - E
 98 E E E E E B - E
 99 A E A E - E - A
 100 E E E E B B - E
 101 E E A C E A A
 102 E E A C E A A -
 103 E A A B B - E
 104 E E B B E A A
 The above-mentioned compounds, including complexes with metal salts, are of interest to be used as agricultural fungicides and, as such, are applicable in various places such as seeds, soils and foliage.

  For such uses, these compounds are applicable in practice in the technical or pure form where they have been prepared, in the form of solutions or in the form of compositions. The agents in question are usually incorporated into a support or vehicle or are presented in the form of compositions which make it possible subsequently to disseminate and distribute them effectively as fungicides. For example, these agents, including their complexes with metal salts, can be presented in the form of wettable powders, emulsifiable concentrates, dusting powders, granular compositions, aerosols or concentrates in fluid emulsions capable of flow. In the case of such compositions, the products can be diluted with a liquid or solid vehicle and, if desired, suitable surfactants can be incorporated therein.



   It is usually desirable, more particularly in the case of compositions for spraying on foliage, to incorporate adjuvants such as wetting agents, spreading agents, dispersing agents, sticky or adhesive agents and the like, in accordance with practices. current agricultural. A list of such commonly used adjuvants can be found in the publication by John W. McCutcheon, Inc .: Detergents and Emulsifiers,
Annual.



   In general, the compounds and complexes in question can be dissolved in certain solvents such as acetone, methanol, ethanol, dimethylformamide, pyridine or dimethylsulfoxide, and the solutions thus obtained are dilutable with water. The concentration by weight of the solution can vary from 1 to 90%, a preferred concentration range extending from 5 to 50%.



   For the preparation of emulsifiable concentrates, the compound can be dissolved in suitable organic solvents, or in a mixture of solvents, together with an emulsifying agent which allows a dispersion of the fungicide in water. The concentration of the active ingredient in emulsifiable concentrates is usually between 10 and 90% and, in concentrates of the flowable emulsion type, it can be as high as 75%.



   Wettable powders, applicable as sprays, can be prepared by mixing the compound with a finely divided solid such as clays, mineral carbonates and silicates, silicas and incorporating wetting agents, sticking agents and / or dispersing agents to such mixtures. The concentration of active ingredients in such compositions is usually between 20 and 98%, preferably between 40 and 75%. A typical wettable powder is prepared by mixing 50 parts of an imidazole derivative of the invention with 45 parts of a synthetic precipitated hydrated silicon dioxide commercially available under the trademark Hi-Sil, and 5 parts of lignosulfonate sodium sold commercially under the trademark Marasperse N-22.

  In another preparation, a clay of the kaolin type (Barden) is used in place of the Hi-Sil in the wettable powder above and, in another such preparation, 25% of the Hi-Sil is replaced by a sodium silicoaluminate. synthetic sold under the trademark Zeolex 7. The above-mentioned parts are parts by weight.



   Powders to be sprinkled are prepared by mixing aralcoylimidazoles or their complexes with metal salts, with finely divided inert solids which can be of organic or mineral nature. Among the materials which can be used for this purpose include botanical flours, silicas, silicates, carbonates and clays. A suitable method for preparing such a dusting powder is to dilute a wettable powder with a finely divided vehicle or carrier. Powder concentrates with 20 to 80% by weight of the active ingredient are commonly produced and are subsequently diluted to a concentration of between 1 and 10% for actual use.



   The imidazole derivatives included in the scope of the invention, including their complexes with metal salts, are applicable as fungicidal sprays by commonly used methods such as conventional hydraulic sprays in large or low volumes, blown sprays. air, aerial spraying, dusting. The dilution and rate of application may depend on the type of equipment used, the method of application, the diseases to be controlled, but the preferred effective proportion is usually between about 0.1 and about 28 kglha (this weight being calculated as an active ingredient).

 

   As a fungicide for the protection of grains or seeds, the proportion of active compound forming a coating on the seeds usually corresponds to approximately 6 to 1250 g / 100 kg of seeds.



  For soil treatment, the fungicide can be incorporated into the soil or applied to its surface, usually at a rate between 0.1 and 56 kg / ha. For application to foliage, the fungicide can usually be applied to growing plants at a rate of 0.1 to 11 kg / ha.



   The fungicides in question can be used in combination with other fungicides or antibiotics, metalliferous or non-metalliferous, in particular those which are known and used in the current state of the art. Among these already known products, the following may be mentioned: a) dithiocarbamates and their derivatives, such as: ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), ethylenebisdithiocarbamate of manganese (maneb) and its product
 coordinating with the zinc ion (mancozeb), zinc ethylenebisdithiocarbamate (zineb), zinc propylenebisdithiocarbamate (propineb), sodium methyldithiocarbamate (metham), tetramethylthiuram (thiram) disulfide, and 3,5-dimethyl-1,3, 5-2H-tetrahydrothiadiazine-2-thione (diazomet); b) nitrophenol derivatives such as:

   dinitro- (1-methylheptyl) phenyl crotonate (dinocap), 2-sec.-butyl4,6-dinitrophenyl 3,3-dimethylacrylate
 (binapacryl), and 2-sec-butyl-4,6-dinitrophenyl and isopropyl carbonate; c) heterocyclic structures such as:
N-trichloromethylthiotetrahydrophthalimide (captan),
N-trichloromethylthiophthalimide (folpet), 2-heptadecyl-2-imidazoline acetate (glyodin), 2-octylisothiazolone-3, 2,4-dichloro-6- (o-chloranilino) -2-triazine, phthalimidophosphorothioate, 4- butyl-1,2,4-triazo, 5-amino-1- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-
 triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadia 2,3-dicyano-1,4-dithiaanthraquinone (dithianon), 2-thio-1,3-dithio- [4,5-b] - quinoxaline (thioquinox),

   1- (methyl butylcarbamoyl) -2-benzimidazolecarbamate
 (benomyl), 244-thiazolyl) benzimidazole (thiabendazole), 4- (2-chlorophenylhydrazono> 3-methyl-5-isoxazolones, pyridine-2-thiol-1-oxide, 8-hydroxyquinoline sulfate, 2,3-dihydro- 5-carboxanilido-6-methyl- 1,4-oxathiin4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, agphenyl) -a- (2,4-dichlorophenyl) -5-pyrimidinylmethanol
 (triarimol), cis-N - [(1,1,2,2-tetrachloroethyl) thio] -4-cyclohexene-1,2
 dicarboximide, 3- [243,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] -
 glutarimide (cycloheximide), dehydroacetic acid,
N- (1,1,2,2-tetrachloroethylthio) -3a, 4,7,4a-tetrahydrophthal
 imide (captafol), 6-butyl-2-ethylamino 91-hydroxy-6-methylpyrimidine (ethirimol),

   4-cyclododecyl-2,6-dimethylmorpholine acetate (dodemorph), and 6-methyl-2-oxo-1,3-dithiolo- [4,5-b] -quinoxaline (quino
 methionate).



  d) various halogenated fungicides such as: tetrachloro-p-benzoquinone (chloranil), 2,3dichloro-1, 4-naphthoquinone (dichlone), 1,3-dichloro-2,5-dimethoxybenzene (chloroneb), acid 3,5, 6-trichloro-o-anisique (tricamba), 2,4,5,6-tetrachloro-isophthalonitrile (TCPN), 2,6-dichloro-4-nitroaniline (dicloran), 2-chloro-1 -nitropropane, polychloronitrobenzenes such as : pentachloronitrobenzene (PCNB), and tetrafluorodichloroacetone; e) fungicidal antibiotics such as: griseofulvin, kasugamycin, and streptomycin; f) copper-based fungicides such as: cuprous oxide, basic culvric chloride, basic copper carbonate, copper naphthenate, and Bordeaux mixture, and g) various fungicides such as:

   diphenyl, dodecylguanidine acetate (dodine), phenylmercuric acetate,
N-ethylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-
 hexachlorophthalimide, phenylmercurimonoethanolammonium lactate, p-dimethylaminobenzenediazosodiumsulfonate, methylisothiocyanate, 1 -thiocyano -2,4-dinitrobenzene, 1-phenylthiosemicarbazide, nickel-containing compounds, calcium cyanamide, sulfur lime, sulfur (and 1,2- methoxycarbonyl-2-thio-ureido) benzene (thio phanatemethyl).

 

   The above-mentioned included metal salt complexes can advantageously be used in various ways. Since the metal salt compounds and complexes in question have an inherent teletoxicity and a broad spectrum of fungicidal activity, they can be used for the storage and preservation of cereal grains. The fungicides in question can also be used for the protection of lawns, lawns, orchards of fruit trees. Other applications of the metal salt compounds and complexes in question will readily come to mind for agricultural and horticultural specialists.


    

Claims (6)

CLAIMS 1. Process for the preparation of an aralcoylimidazole substituted in position 1, of formula: EMI1.1 in which Z1 is a C6 to C14 aryl radical or a substituted C6 to C14 aryl radical; R1 is a hydrogen atom, a C1 to C10 alkyl radical; a C2 to C12 alkenyl radical; a C7 to C9 aralkyl radical which may be substituted; a phenyl radical which may be substituted, a C3 to C7 cycloalkyl radical, OR a C5 to C7 cycloalkenyl radical; R2 is a C1 to C1o alkyl radical, a C2 to C12 alkenyl radical, a C7 to C9 aralkyl radical which may be substituted; a phenyl radical which may be substituted; RIÚ and R?, Taken together, can form a C3-C8 cycloalkyl radical; A and B are divalent C1 to C5 alkylene radicals; X1 is a C1 to C4 alkyl radical, a halogen atom or a nitro radical; al is an integer from 0 to 3; n is an integer equal to 0 or 1 n 'is an integer equal to 0 or 1; and the sum of n + n 'is 1 or 2; or, when ZI is an unsubstituted phenyl radical, RIÚ is a hydrogen atom, A is methylene, and n 'is O, then R? is a C4 to C10 alkyl radical, a C2 to C12 alkenyl radical, a C7 to Cg aralkyl or C7 to Cg aralkyl radical, a phenyl or substituted phenyl radical, a cycloalkyl radical C3 to C7 OR a C5 to C7 cycloalkenyl radical; with the condition that, when R1 and R, 2 are both hydrogen, n + n 'is 1 or 2; and with the additional condition that, when ZI is phenyl (C6H5) and RIÚ, RIê and RI are hydrogen, RI4 is different from a C1 to C3 alkyl, and the addition salts with agronomically acceptable acids of the derivatives in question , characterized in that a derivative of formula is reacted EMI1.2 in which W is a halogen, a C1 to C4 alkyl sulfonate, benzenesulfonate or toluenesulfonate, and ZI, A, n, RIÚ to R ?, B and n 'are as defined above with an appropriate imidazole derivative or a salt of this derivative. 2. Method according to claim 1, characterized in that said imidazole derivative or the salt of this derivative is used in substantially equimolecular amounts or in excess relative to the equimolecular amount. 3. Method according to claim 2, characterized in that the reaction is carried out in an inert solvent. 4. Method according to claim 1, characterized in that the imidazole derivative of formula III is reacted with a metal salt in the form of free base or of addition salt with an acid to obtain a complex metal salt of formula EMI1.3 in which the substituents Z ,, R1 to R ?, A, B, XI, n, n 'et al have the same meanings as in formula III above, M is a metal cation which can be chosen from groups IIA , IVA, VA, IB, IIB, VIA, VIIA and VIII of the periodic table, Y is a solubilizing antagonist anion and m is a number from 1 to 4. 5. Use of the alkyllimidazole derivative obtained according to claims 1 and 4, as a fungicidal agent. 6. Aralcoylimidazole substituted in position 1, obtained by the process according to claim 1. The invention relates to a process for the preparation of an aralkoylimidazole substituted in position 1 and to its application as a fungicidal agent. This substituted aralcoylimidazole corresponds to the formula: EMI1.4 in which Z1 is a C6 to C14 aryl radical or a substituted C6 to C14 aryl radical; RIÚ is a hydrogen atom, a C1 to C10 alkyl radical; C12 to C12 unradicalalkenyl; a C7 to C9 aralkyl radical which may be substituted; a phenyl radical which may be substituted, a C3 to C7 cycloalkyl radical, or a C5 to C7 cycloalkenyl radical; R? is a C1 to C1o alkyl radical, a C2 to C12 alkenyl radical, a C7 to Cs aralkyl radical which may be substituted; a phenyl radical which may be substituted; R1 and R2, taken together, can form a C3 to C8 cycloalkyl radical; A and B are divalent C1 to C5 alkylene radicals; X1 is a C1 to C4 alkyl radical, a halogen atom or a nitro radical; ai is an integer from O to 3; n is an integer equal to O or 1; n 'is an integer equal to o or 1; and the sum of n + n 'is 1 or 2; or, when Z, is an unsubstituted phenyl radical, RIÚ is a hydrogen atom, A is methylene, and n 'is O, then R? is a C4 to C1O alkyl radical, a C2 to C12 alkenyl radical, a C7 to C9 aralkyl or C7 to C6 substituted aralkyl radical, a phenyl or substituted phenyl radical, a C3 to C7 cycloalkyl radical or a C3 to C7 cycloalkenyl radical; with this condition that, when RIÚ and R? are both hydrogen, n + n 'is 1 or 2; and with the additional condition that, when ZI is phenyl (C6H8) and Rt, RIê and R31 are hydrogen, Rt is different from C1 to C3 alkyl and the addition salts with agronomically acceptable acids of the derivatives in question. ** ATTENTION ** end of the CLMS field may contain start of DESC **.