Accordingly, a need exists in the art for an improved process for the preparation of 1,4-diaryl-2-fluoro-1,3- butadiene compounds which avoids the use of phosphonium halide compounds.

It is, therefore, an object of the present invention to provide new compounds which are useful in the preparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds.

It is also an object of the present invention to provide an improved process for the preparation of 1,4- diaryl-2-fluoro-1,3-butadiene compounds which avoids the use of phosphonium halide compounds.

It is a further object of this invention to provide an improved process for the preparation of 1,4- diaryl-2-fluoro-2-butene compounds.

Other objects and advantages of the present invention will be apparent to those skilled in the art from the description below and the appended claims.

SUMMARY OF THE INVENTION The present invention provides 1,4-diaryl-2- fluoro-1-buten-3-ol compounds of the structural formula I wherein R is hydrogen, C1-C4alkyl, C1-C4haloalkyl, C3- C6cycloalkyl or C3-C ; halocycloalkyl; Ar is phenyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C.-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups, 1-or 2-naphthyl optionally substituted with any combination of from one to three halogen, Cl-C4alkyl, C1-C4haloalkyl Cl-C4alkoxy or cl-chaloalkoxy groups, or a 5-or 6-membered heteroaromatic ring optionally substituted with any combination of from one to

three halogen, C1-C4alkyl, C1-C4haloalkyl, C,-C4alkoxy or C'halcalkoxy groups; and Arl is phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, Cl-C4haloalkyl, C1-CQalkoxy or C1-C4haloalkoxy groups, phenyl optionally substituted with any combination of from one to five halogen, C-C4alkyl, C,-C4haloalkyl, Cl-C4alkoxy or C-C4haloalkoxy groups, biphenyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups, phenoxypyridyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, Cl-C4haloalkyl, C1-CQalkoxy or Cl-C4haloalkoxy groups, benzylpyridyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, C1-C4haloalkyl, Cl-C4alkoxy or C1-C4haloalkoxy groups, benzylphenyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxyor Cl-C4haloalkoxy groups, benzoylphenyl optionally substituted with any combination of from one to five halogen, Cl-Cqalkyl, Cl-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups, 1-or 2-naphthyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or Cl-C4haloalkoxy groups, or

a 5-or 6-membered heteroaromatic ring optionally substituted with any combination of from one to three halogen, C.-C4alkyl, Cl-CQhaloalkyl, Cl-C4alkoxy or C.-C4haloalkoxy groups.

The present invention also provides a new process for the preparation of 1,4-diaryl-2-fluoro-1,3- butadiene compounds of the structural formula II wherein R is hydrogen, C1-C4alkyl, C1-C4haloalkyl, C3- C6cycloalkyl or C3-C6halocycloalkyl; Ar is phenyl optionally substituted with any combination of from one to three halogen, C,-C, alkyl, Cl-C4haloalkyl,.-C4alkoxy or Cl-C4haloalkoxy groups, 1-or 2-naphthyl optionally substituted with any combination of from one to three halogen, C,-C4alkyl, Cl-C4haloalkyl Cl-C4alkoxy or Cl-C4haloalkoxy groups, or a 5-or 6-membered heteroaromatic ring optionally substituted with any combination of from one to three halogen, Cl-C4alkyl, C1-C4haloalkyl, Cl-C4alkoxy or C.-C4haloalkoxy groups; and Arl is phenoxyphenyl optionally substituted with any combination of from one to six halogen, Cl-C4alkyl, C1-Cshaloalkyl, C,-Cqalkoxy or

C,-C4haloalkoxy groups, phenyl optionally substituted with any combination of from one to five halogen, C,-C, alkyl, C1-C4haloalkyl, C1-C4alkoxy or Cl-C4haloalkoxy groups, biphenyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, C1-C4haloalkyl, C,-C4alkoxy or C,-C, haloalkoxy groups, phenoxypyridyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, Cl-C4haloalkyl, Ci-C4alkoxy or C1-C4haloalkoxy groups, benzylpyridyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cz-C4haloalkoxy groups, benzylphenyl optionally substituted with any combination of from one to five halogen, C,-c4alkyl, C,-C, haloalkyl, C'-C4alkoxy or Cl-Cqhaloalkoxy groups, benzoylphenyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or Cl-C4haloalkoxy groups, 1-or 2-naphthyl optionally substituted with any combination of from one to three halogen, C,-CQalkyl, Cl-C4haloalkyl, C,-C9alkoxy or Cl-C4haloalkoxy groups, or a 5-or 6-membered heteroaromatic ring optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, Cl-C4alkoxy or C-Chaloalkoxy groups, which process comprises reacting a 1,4-diaryl-2-fluoro- 1-buten-3-ol compound of the structural formula I

wherein Ar, Ar, and R are as hereinbefore defined with a sulfonyl chloride or sulfonic acid anhydride compound and a base.

The present invention further provides a new process for the preparation of 1,4-diaryl-2-fluoro-2- butene compounds having the structural formula III wherein R is hydrogen, C-CalkyI,C-ChaloalkyI,C- C6cycloalkyl or C3-C6halocycloalkyl; Ar is phenyl optionally substituted with any combination of from one to three halogen, C,-C, alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups, 1-or 2-naphthyl optionally substituted with any combination of from one to three halogen, C,-c4alkyl, Cl-C4haloalkyl Cl-C4alkoxy or Cl-C4haloalkoxy groups, or a 5-or 6-membered heteroaromatic ring optionally

substituted with any combination or from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, c,-c4alkoxy or halcalkoxy groups; and Arl is phenoxyphenyl optionally substituted with any combination of from one to six halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups, phenyl optionally substituted with any combination of from one to five halogen, C,-C, alkyl, C1-C4haloalkyl, C1-C4alkoxy or C.-C, haloalkoxy groups, biphenyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, Cl-C4haloalkyl, C1-CQalkoxy or C,-C4haloalkoxy groups, phenoxypyridyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or C1-C4haloalkoxy groups, benzylpyridyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or Ci-C4haloalkoxy groups, benzylphenyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups, benzoylphenyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, Cl-C4haloalkyl, C,-C4alkoxy or Cl-C4haloalkoxy groups, 1-or 2-naphthyl optionally substituted with any combination of from one to three halogen,

C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxyor Cl-C1haloalkoxy groups, or a 5-or 6-membered heteroaromatic ring optionally substituted with any combination of from one to three halogen, C-C4alkyl, C-C4haloalkyl, ci-c-, alkoxy or C-C4haloalkoxy groups, which process comprises: (a) reacting a 1,4-diaryl-2-fluoro-1-buten-3-ol compound of the structural formula I

wherein Ar, Arl and R are as described above with a sulfonyl chloride or sulfonic acid anhydride compound and a base to form a 1, 4-diaryl-2-fluoro-1, 3-butadiene compound of the structural formula II

(b) reacting the 1,4-diaryl-2-fluoro-1,3-butadiene compound with: (1) an alkaline earth metal in the presence of a protic solvent, or (2) an alkali metal in the presence of an aprotic solvent.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1,4-diaryl-2- fluoro-l-buten-3-ol compounds having the structural formula I wherein Ar, Ar, and R are as described hereinbefore defined.

Preferred formula I compounds of this invention are those wherein R is C1-C4alkyl, C1-C4haloalkyl, C1-C6cycloalkyl or C,-C6halocycloalkyl ; Ar is phenyl optionally substituted with any combination of from one to three halogen, Cl-C4alkyl, C1-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups; and Ar, is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, Cl-C4alkyl, C1-C4haloalkyl, Cl-C4alkoxy or C,-C4haloalkoxy groups, 3-biphenyl optionally substituted with any combination of from one to five halogen, C1-CQalkyl, Cl-C4haloalkyl, Cl-Calkoxy or c,-c4haloalkoxy groups, or 3-benzylphenyl optionally substituted with any combination of from one to five halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or Cl-C4haloalkoxy groups.

More preferred 1,4-diaryl-2-fluoro-1-buten-3-ol compounds of this invention are those

wherein R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups; and Arl is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, C,-C4haloalkyl, C.-C4alkoxy or C.-C4haloalkoxy groups.

1- (p-Chlorophenyl)-1-cyclopropyl-2-fluoro-4- (4- fluoro-3-phenoxyphenyl)-1-buten-3-ol and 1-(a, a,- trifluoro-p-tolyl)-1-cyclopropyl-2-fluoro-4- (4-fluoro- 3-phenoxyphenyl)-1-buten-3-ol are especially useful for the preparation of highly active insecticidal and acaricidal agents of formula III.

In formulas I, II and III above, the 5-and 6- membered heteroaromatic ring may suitably be a ring containing one to four heteroatoms selected from N, O and S, wherein the heteroatoms may be the same or different, e. g. the rings include, but are not limited to, pyridyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, tetrazolyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thienyl and thiazolyl rings each optionally substituted as described in formulas I, II and III above.

Exemplary of"halogen"hereinabove are fluorine, chlorine, bromine and iodine. The terms"C,- C4haloalkyl","C3-Cshalocycloalkyl"and"Cl-C4haloalkoxy" are defined as a Cl-C4alkyl group, a C3-C6cycloalkyl group and a C-C4alkoxy group substituted with one or more halogen atoms, respectively, wherein the halogen atoms may be the same or different.

When used herein as a group or part of a group, the term"alkyl"includes straight or branched chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl.

When used herein as a group or part of a group, the term"cycloalkyl"includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Groups containing two or more rings, such as phenoxyphenyl, phenoxypyridyl, biphenyl and benzylphenyl, which may be substituted, may be substituted on either ring unless otherwise specified herein.

In a preferred embodiment of the present invention, the 1, 4-diaryl-2-fluoro-1, 3-butadiene compounds of formula II are prepared by reacting a 1,4- diaryl-2-fluoro-1-buten-3-ol compound of formula I with a sulfonyl chloride or sulfonic acid anhydride compound and a base, preferably at a temperature ranging from about-78°C to 120°C, more preferably from about 20°C to 80°C, in the presence of a solvent.

In another preferred embodiment of the present invention, the 1, 4-diaryl-2-fluoro-2-butene compounds of formula III are prepared by reacting a 1,4-diaryl-2- fluoro-1-buten-3-ol compound of formula I with a sulfonyl chloride or sulfonic acid anhydride compound and a base, preferably at a temperature ranging from about-78°C to 120°C, more preferably from about 20°C to 80°C, in the presence of a solvent to form a 1,4- diaryl-2-fluoro-1,3-butadiene compound of formula II, and reacting the formula II butadiene compound with an alkaline earth metal in the presence of a protic solvent.

Advantageously, the present invention provides a process for the preparation of 1, 4-diaryl-2-fluoro-1, 3-

butadiene compounds which avoids the use of phosphonium halide compounds.

The product formula and III compounds may be isolated by diluting the reaction mixture with water and extracting the product with a suitable extraction solvent. In the isolatic-procedure, conventional extraction solvents such as diethyl ether, ethyl acetate, toluer, e, methylene chloride, and the like, and mixtures thereof may be utilized.

Sulfonyl chloride compounds suitable for use in the present invention include, but are not limited to, unsubstituted and substituted phenylsulfonyl chlorides such as p-toluenesulfonyl chloride and the like, C,-C6alkylsulfonyl chlorides such as methanesulfonyl chloride and the like, and Cl-C6haloalkylsulfonyl chlorides such as trifluoromethanesulfonyl chloride and the like. Sulfonic acid anhydrides suitable for use in this invention include, but are not limited to, unsubstituted and substituted phenylsulfonic acid anhydrides such as p-toluenesulfonic acid anhydride and the like, Cl-CSalkylsulfor. ic acid anhydrides such as methanesulfonic acid anhydride and the like, and Cl-C6haloalkylsulfonic acid anhydrides such as trifluoromethanesulfonic acid anhydride and the like.

Bases suitable for use in the present invention include, but are not limited to, alkali metal hydrides such as sodium hydride, potassium hydride, lithium hydride and the like, alkaline earth metal hydrides such as calcium hydride and the like, alkali metal Ci- C6alkoxides such as sodium methoxide, potassium t- butoxide and the like, C-C6alkyllithiums such as n- butyllithium, sec-butyllithium, methyllithium and the like, and lithium dialkylamides such as lithium diisopropylamide, lithium isopropylcyclohexylamide and

the like. Preferred bases include alkali metal hydrides.

Solvents suitable for use in the preparation of the formula II and III compounds of this invention include, but are not limited to, ethers such as tetrahydrofuran, dioxane, pyran, diethyl ether, 1,2- dimethoxyethane and the like; carboxylic acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and the like; dialkyl sulfoxides such as dimethyl sulfoxide and the like; nitriles such as acetonitrile, propionitrile and the like; aromatic hydrocarbons such as toluene, benzene, xylenes, mesitylene and the like; and halogenated aromatic hydrocarbons such as chlorobenzene, fluorobenzene and the like; and mixtures thereof. Preferred solvents for use in the preparation of the formula II and III compounds include ethers.

Protic solvents suitable for use in this invention include, but are not limited to, Cl-C6alcohols such as methanol, ethanol and the like. Preferred protic solvents include methanol and ethanol. Aprotic solvents include, but are not limited to, ammonia; and ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane and the like.

Alkaline earth metals suitable for use in the preparation of the formula III compounds include, but are not limited to, magnesium and calcium with magnesium being preferred. Alkali metals include, but are not limited to, lithium, sodium and potassium.

Preferred formula II and III compounds which may be prepared by the processes of this invention are those wherein R is C,-C4alkyl, Cl-Chaloalkyl, C,-C6cycloalkyl or C3-C6halocycloalkyl ; Ar is phenyl optionally substituted with any combination

of from one to three halogen, alkyl, C-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups; and Arl is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, C.-C4alkyl, Cl-C4haloalkyl, C,-Cyalkoxy or Cl-C4haloalkoxy groups, 3-biphenyl optionally substituted with any combination of from one to five halogen, C.-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or C-C4haloalkoxy groups, or 3-benzylphenyl optionally substituted with any combination of from one to five halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups.

More preferred 1, 4-diaryl-2-fluoro-1, 3-butadiene and 1,4-diaryl-2-fluoro-2-butene compounds which may be prepared by the processes of this invention are those wherein R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of from one to three halogen, Cl-C4alkyl, C-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups; and Arl is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy or Cl-C4haloalkoxy groups.

The present invention is especially useful for the preparation of 1-(p-chlorophenyl)-l-cyclopropyl-2-fluoro-4-(4-fluoro- 3- phenoxyphenyl)-1,3-butadiene;

l-(atata-trifluoro-p-tolyl)-l-cyclopropyl-2-luoro-4 (4-fluoro-3-phenoxyphenyl)-1,3-butadiene; 1- l- (a, a, a-trifluoro-p-tolyl)-2-fluoro-4- (4-fluoro-3- phenoxyphenyl)-2-butenyl cyclopropane; and 1- l- (p-chlorophenyl)-2-fluoro-4- (4-fluoro-3-phenoxy- phenyl)-2-butenyl cyclopropane.

The present invention further provides a process for the preparation of 1,4-diaryl-2-fluoro-1-buten-3-ol compounds of formula I which process comprises: (a) reacting an arylmethanebromide compound of the structural formula IV ArlCH2Br (IV) wherein Arl is as described hereinabove with a lithium Cl-C6alkyltellurolate compound to form an intermediate compound of the structural formula V ArlCH2TeLi (V) (b) reacting the formula V intermediate compound with a C,-C, alkyllithium compound to form an intermediate compound of the structural formula VI Ar1CH2Li; and (VI) (c) reacting the formula VI intermediate compound with a 3-aryl-2-fluoropropenal compound of the structural formula VII

wherein R and Ar are as hereinbefore defined.

In a preferred embodiment of the present invention, the 1,4-diaryl-2-fluoro-1-buten-3-ol compounds of formula I are prepared by reacting an arylmethanebromide compound of formula IV with a lithium Cl-C6alkyltellurolate compound, preferably at a temperature ranging from about-78°C to about 30°C, more preferably from about-78°C to about 0°C, in the presence of a soiCW Wim, dn intermediate compound of formula V, reacting the formula V intermediate compound in situ with a Cl-C6alkyllithium compound, preferably at a temperature ranging from about-78°C to about 30°C, more preferably from about-78°C to 0°C, to form an intermediate compound having the structural formula VI, and reacting the formula VI intermediate compound in situ with a 3-aryl-2-fluoropropenal compound of formula VII, preferably at a temperature ranging from about-78°C to about 30°C.

Lithium C1-C6alkyltellurolate compounds suitable for use in the present invention include, but are not limited to, lithium n-butyltellurolate, lithium sec- butyltellurolate, lithium t-butyltellurolate, lithium n-propyltellurolate and the like. C,-C,, alkyl lithium compounds suitable for use include, but are not limited to, n-butyllithium, sec-butyllithium, n-propyllithium, methyllithium and the like.

Solvents useful in the preparation of the formula I compounds of this invention include, but are not limited to, ethers such as diethyl ether,

tetrahydrofuran, 1,2-dimethoxyethane and the like and mixtures thereof, with tetrahydrcfuran being preferred.

In order to facilitate a further understanding of this invention, the following examples are presented primarily for the purpose of illustrating more specific details thereof. The scope of the invention should not be deemed limited by the examples but encompasses the entire subject matter defined in the claims.

EXAMPLE 1 Preparation of l- (p-Chlorophenvl)-l-cyclopropvl-2- fluoro-4- (4-fluoro-3-henoxvnhenyl)-l-buten-3-ol

A solution of lithium n-butyltellurolate (10.5 mmol, n-BuTeLi), generated in situ from n-butyllithium (4.2 ml of 2.5 M solution in hexane, 10.5 mmol) and Te powder (1.34 g, 10.5 mmol) in tetrahydrofuran (10 ml) at 0°C, is treated with a solution of 3-phenoxy-4- fluorobenzyl bromide (2.81 g, 10 mmol) in tetrahydrofuran (10 ml) at 0°C, stirred for 30 minutes, cooled to-78°C, treated with a solution of n- butyllithium (4.2 ml of 2.5 M solution in hexane, 10.5

mmol), stirred for 30 minutes at-78°C, treated with a solution of p-chloro-ß-cyclopropyl-a- fluorocinnamaldehyde (2.24 g, 10 mmol) in tetrahydrofuran (5 ml), warmed to room temperature with stirring for 3 hours, quenched with 2 N hydrochloric acid, and extracted with ethyl acetate. The combined organic extracts are washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a residue. Flash chromatography of the residue on silica gel using a 1: 4 ethyl acetate/hexanes solution gives the title product (3.5 g, 82% yield) which is identified by lH, 19F and 13C NMR spectral analyses.

Following essentially the same procedure, but using p-(trifluoromethyl)-5-cyclopropyl-a- fluorocinnamaldehyde, 1-(a, a, a-trifluoro-p-tolyl)-1- cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl)-1- buten-3-ol is obtained.

EXAMPLE 2 Preparation of 1- (p-Chlorophenvl)-l-cyclopropvl-2- fluoro-4- (4-fluoro-3-phenoxvphenyl)-1, 3-butadiene

A suspension of sodium hydride (6.3 mg, 0.26 mmol) in tetrahydrofuran (1 ml) is treated with a solution of 1- (p-chlorophenyl)-1-cyclopropyl-2-fluoro-4- (4-fluoro- 3-phenoxyphenyl)-1-buten-3-ol (106.7 mg, 0.25 mmol) in tetrahydrofuran (1.5 ml), stirred at 50°C for 10 minutes, cooled to room temperature, treated with a solution of p-toluenesulfonyl chloride (49.6 mg, 0.26 mmol) in tetrahydrofuran (1 ml), stirred at 60 °C for 1 hour, quenched with water, and extracted with ethyl acetate. The combined organic extracts are washed sequentially with water, saturated sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and concentrated in vacuo to obtain a residue. Flash chromatography of the residue using silica gel and a 1: 9 ethyl acetate/hexanes solution

gives the title product (62 mg, 61% yield) which is identified by iH, 19F and 13C NMR spectral analyses.

Following essentially the same procedure, but using 1- (a, a, a-trifluoro-p-tolyl)-l-cyclopropyl-2- fluoro-4- (4-fluoro-3-phenoxyphenyl)-1-buten-3-ol, 1- (a,a, a-trifluoro-p-tolyl)-1-cyclopropyl-2-fluoro-4- (4- fluoro-3-phenoxyphenyl)-1,3-butadiene is obtained.