MXPA97003752A - Process and intermediate compounds for the preparation of fluoroolefi pesticide compounds - Google Patents

Abstract

The present invention relates to: A process and intermediate compounds for the preparation of fluoroolefin compounds that are useful as pesticidal agents

Description

PROCESS AND INTERMEDIATE COMPOUNDS FOR THE PREPARATION OF COMPOUNDS PESTICIDES OF FLUOROOLEPHINS BACKGROUND OF THE INVENTION Fluoroolefin compounds that are useful as pesticidal agents are described in WO 94/06741 and GB 2,288.8 03-A. Those references. they also describe processes for the preparation of fluoroolefin compounds. However, these processes are not completely satisfactory because the fluoroolefin compounds are produced in relatively low yie These references also do not teach how to make the intermediates of the present invention.

SUMMARY OF THE INVENTION The present invention provides an effective and efficient process for the preparation of a pesticidal fluo-roolefin compound having the structural formula I (I) REF: 24569 wherein R is hydrogen, or C 1 -C 4 alkyl, and R 1 is C 1 -C 4 alkyl, or cycloprolyl, or R and R are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C alquilo-C alquilo alkyl, C.-C.haloalkyl, C.-C. alkoxy, or c 1-4-haloalkoxy, or 1- or 2- naphthyl optionally substituted with any combination of from one to three halogen groups, C 1 -C 4 alkyl, C 1 -C haloalkyl, C 1 -C 6 alkoxy, or haloalkoxy Ar 1 is phenoxyphenyl optionally substituted with any combination of from one to five halogen / C 1 -C alkyl groups. , haloalkyl ^ -C., alkoxy C.-C., or haloalco¬ biphenyl optionally substituted with any combination of from one to five halogen groups, C-C alkyl, C-C haloalkyl, C-C alkoxy. or haloalkoxy C ..- C., benziphenyl optionally substituted with any combination of from one to five halogen groups, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 5 alkoxy, or C 1 -C 4 haloalkoxy, or benzoylphenyl optionally substituted with any combination of from one to five halogen groups, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, or C.sub.1 -C.sub.4 haloalkoxy, and the configuration of the R.sub.CRR.sup.- groups. and -CH-Ar .. on the double bond is predominantly mutually trans, whose process is characterized in that it reacts a 4-aryl-2-fluoro-2-tuta »-l-ol compound having the structural formula II (ID wherein Ar, R, and R-, are as described above, with a brominating agent, to form a 4-aryl-1-bromo-2-fluoro-2-bubar compound having the structural formula III (III) wherein Ar, R, and R. are as described above, and reacting the compound of formula III with a palladium catalyst, a base, and a boron acid having the structural formula IV, an anhydride of boron having the structural formula V, or a borate ester having the structural formula VI (HO) 2B-Ar? (IV) Ar. .B. O i -B, • B Ar. Ar. (V) (R20) 2 -Arl (VI) wherein R2 is C1-C4 alkyl, and Ar1 is as described above. The present invention furthermore relates to the intermediate compounds 4-aryl-1-bromo-2-fluoro-2-butene of formula III.

Therefore, it is an object of the present invention to provide an effective and efficient process for the preparation of pesticidal fluoroolefin compounds. Furthermore, it is an object of the present invention to provide intermediate compounds which are useful for the preparation of pesticidal fluoroolefin 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.

DETAILED DESCRIPTION OF THE INVENTION A preferred form of the present invention comprises reacting a 4-aryl-2-fluoro-2-butene-1-ol of formula II, with at least about one molar equivalent of a brominating agent, preferably on a scale of temperature of about 50 ° C to 130 ° C, in the presence of a first solvent, to form a 4-aryl-l-bromo-2-fluoro-2-bjbax) of formula III, and reacting the compound of formula III with about 0.001 to 0.1, preferably about 0.005 to 0.1, molar equivalent of a palladium catalyst, at least about 2 molar equivalents, often about 2- 6 molar equivalents of a base, and a boron acid on a temperature scale of about 50 ° C to 130 ° C, in the presence of a second solvent. The present invention furthermore relates to the 4-aryl-l-bromo-2-fluoro-2-butene compounds which are used in the process of this invention. The compounds 4-aryl-l-bromo-2-fluoro-2-but - do not have structural formula III (III) wherein R is hydrogen, or C, -C4 alkyl, and R. is C, -C4 alkyl, or cyclopropyl, or R and R1 are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 4 -C 4 alkoxy, or haloalkyl. i- or 2-naphthyl optionally substituted with any combination of from one to three halogen groups, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl C 1 -C 5 alkoxy, or haloalkoxy cL-c 4; the configuration of the Ar CRR groups. - and - CH2 Br on the double bond is predominantly mutually trans. Exemplary of the aforementioned halogens are fluorine, chlorine, bromine, iodine. The terms "haloalkyl C-C", and "haloalkoxy C-C" are defined as a C.sub.1 -C.sub.4 alkyl group and a C.sub.4 -C.sub.4 alkoxy group substituted with one or more halogen atoms, respectively. The compounds of formula I of the product can be isolated by diluting the reaction mixture with water, and extracting the product with a suitable extraction solvent. In the isolation process, conventional extraction solvents, such as ether, ethyl acetate, methylene chloride, and the like can be used. Suitable brominating agents for use in the process of this invention include, but are not limited to, bromine / triphenyl-phosphine complexes, phosphorus tribromide, thionyl bromide, concentrated hydrobromic acid, and the like, and mixtures thereof. same. Bromine / triphenyl phosphine complexes are preferred brominating agents. The first solvents suitable for use in the present invention include, but are not limited to, aromatic hydrocarbons such as toluene, benzene, xylenes, isothylene, and the like, halogenated aromatic hydrocarbons, such as chlorobenzene, fluorobenzene, and the like, amides of carboxylic acid such as N, -dimethylformamide and the like, ethers such as tetrahydrofarane, dioxane and the like, and halogenated hydrocarbons such as chloroform, carbon tetrachloride and the like, and mixtures thereof. Preferred first solvents include halogenated hydrocarbons, with carbon tetrachloride being the most preferred. The second solvents useful in the process of this invention include, but are not limited to, aromatic hydrocarbons such as toluene, benzene, xylenes, mesitylene, and the like, halogenated aromatic hydrocarbons, such as chlorobenzene, and the like, carboxylic acid amides such as N, N dimethylformamide and the like, glycols such as dimethoxyethane and the like, C, -C4 alcohols such as methanol, ethanol, and the like, ketones such as acetone and the like, and ethers such as tetrahydrofuran, dioxane, and the like, and mixtures thereof, and mixtures with water. Preferred second solvents include aromatic hydrocarbons and mixtures of aromatic hydrocarbon / C1-C4 alcohol, with a mixture of toluene / ethanol being more preferred. Palladium catalysts suitable for use in the present invention include, but are not limited to, palladium (0) catalysts such as bis (dibenzylidene ketone) palladium (O), tetrakis (triphenylphosphine) palladium (0), and the like, catalysts of palladium (II) such as bis (acetonitrile) palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, [1,4-bis (diphenylphosphine) butane] palladium (II) dichloride, [1,1'-bis ( diphenylphosphino) ferrocene] palladium (II) diacetate, palladium (II) acetate, palladium (II) cluride, and the like, and palladium on activated carbon, and mixtures thereof. Preferred catalysts include palladium (0) catalysts, with bis (dibenzylideneacetone) palladium (O) being more preferred. ' Suitable bases for use in this invention include, but are not limited to, alkali metal carbonates, such as sodium carbonate and potassium carbonate, alkaline earth metal carbonates, such as calcium carbonate and the like, alkali metal hydrogen carbonates. , such as sodium hydrogen carbonate and the like, metal hydroxides such as sodium hydroxide, and potassium hydroxide, alkaline earth metal hydroxides, such as calcium hydroxide and the like, C.-C alkoxides, alkali metals such as potassium terbutoxide and the like, thallium carbonate (I), C.-C- thallium alkoxides (I) , thallium hydroxide (I), and tri (C, C4) alkyl amines, such as tri ethylamide, and mixtures thereof. Preferred bases include alkali metal carbonates, with potassium carbonate being more preferred. In another preferred form of the present invention. a 4-aryl-l-bromo-2-fluoro-2-bbbato of formula III is reacted with a palladium catalyst, a base and a boron acid of formula IV. The boron acids of formula IV, boron anhydrides of formula V, and borate esters of formula VI can be prepared, as illustrated in Flow Chart I, by reacting an aryl compound of formula VII with a tri (alkyl). -C ^) borate of formula VIII, to form the borate ester of formula VI, and hydrolyzing the borate ester of formula VI with aqueous acid to form the boron acid of formula IV, which can combine spontaneously with other compounds of Formula IV to form the boron anhydride of formula V.

FLOW DIAGRAM I Ar-M (VII) (M = Li or MgBr) B (OR2) 3 (VIII) (R20) 2B-Ar? (SAW) H30 (HO) 2B-Ar? (IV) -H20 or "B-or Ar and B- .B. Ar. (V) The initial 4-aryl-2-fluoro-2-butan-1-ol compounds of formula II can be prepared according to the procedures described in WO 94/06741 and GB 2,288,803-A. In another preferred form of the present invention. a 4-aryl-2-fluoro-2-tutEnD-l-ol of formula II reacts with a brominating agent in a temperature range from about 50'C to 130"C, and a 4-aryl-1-bromo- 2-fluoro-2-butane of formula III is reacted with a palladium catalyst, a base, and a compound of formula IV, V, or VI in a temperature range of about 50 * C to 130 ° C. Preferred fluoroolefin of formula I that can be prepared by the process of this invention are those wherein R is hydrogen, and R ^ is isopropyl or cyclopropyl, or R and R1 are methyl, or R and R1 are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C1-C4 alkyl, haloalkyl C.-C4, alkoxy C.-C ^, , or haloalkoxy W and Ar., Is 3-phenoxyphenyl optionally substituted with any combination of from one to five halogen groups, C 1 Cj alkyl, C 1 -C 4 haloalkyl, C 1 -C alkoxy, haloalkoxy 3-biphenyl optionally substituted with any combination of from one to five halogen groups, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or haloalkoxy C.-C 3 3 benzyl-lupine substituted with any combination of from one to five halogen groups, C ..-C4 alkyl, haloalkyl C.-C ^ alkoxy C, -C4, or haloalco xi C1-C4, or 3-benzoylphenyl optionally substituted with any combination of from one to five halogen groups, C, -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or haloalkoxy c 1 -C 4. The process of the present invention is also preferentially used for the preparation of pesticidal fluoroolefins of formula I, wherein R and R1 are methyl, or R and R. are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C, -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy and Ar 1 is 3-phenoxyphenyl optionally substituted with any combination of from one to five halogen groups, C1-C4 alkyl, haloalkyl C.-C4, alkoxy C ..-C., or haloalkoxy Cj-C .. To facilitate further understanding of the invention, the following examples are presented , mainly for the purpose of illustrating more specific details of it. The field of the invention should not be construed as limited by the examples, but encompasses the entire subject matter defined in the claims.

EXAMPLE 1 Preparation of l- (p-Chlorophenyl) -! - (3-bromo-2-fluoropropionyl) cyclopropane, (Z) - c Under a nitrogen atmosphere, a solution of bromine (0.767 g, 4.8 mmol) in carbon tetrachloride at an ice-water bath temperature is treated sequentially with a solution of triphenylphosphine (1.26 g, 4%). , 8 mmol) in carbon tetrachloride, and a solution of 3- [l- (p-chlorophenyl) -cyclopropyl] -2-fluoro-2-propen-1-ol, (Z) - (0.907 g, 4 mmol) in carbon tetrachloride is heated and stirred at reflux for 70 minutes, cooled to room temperature, and poured into petroleum ether. The resulting mixture is filtered, and the filtrate is concentrated in va-cuo to obtain a residue. The residue is dissolved in petroleum ether and passed through a plug of silica gel (eluted with hexanes) to obtain an oil. Flash column chromatography of the oil, using silica gel and a 3:20 methylene chloride / hexanes solution, gives the title product as a colorless oil (0.73 g, * 63% product), which is identified by NMR spectrum analysis.

EXAMPLE 2 Preparation of 1- (p-chloro phenyl) -! - [2-f luoro-3- (4-f luoro-3-phenoxyphenyl) propenyl T-cyclopropane. (Z) - Under a nitrogen atmosphere, a mixture of 1- (p-chlorophenyl) -l- (3-bromo-2-fluoropropenyl) cyclopropane, (Z) - (0.434 g, 1.5 mmol), 4-fluoro- 3-phenoxybenzene-lObcßjí-D (0.452 g, 1.95 mmol), potassium carbonate (1.86 g, 13.5 mmol); and bis (dibenzylideneacetone) -palladium (O) (Pd (dba) -, 4.3 mg, 0.075 mmol) in toluene, is heated at 80 ° C for one hour, cooled to room temperature, diluted with water, and filtered at room temperature. through the diatomaceous earth.

The phases are separated and the aqueous phase is extracted with ethyl acetate. The organic phase and the ethyl acetate extract are combined, washed with water, dried over anhydrous sodium sulfate, and concentrated in vacuo to obtain a residue. Flash column chromatography of the The residue, using silica gel and a 3:20 methylene chloride / hexanes solution, gives the title product as an oil (0.274 g, 63% product), which is identified by NMR spectrum analysis. As can be seen from the data of the Examples 1 and 2, 1- (p-chlorophenyl) -l- [2-fluoro-3- (4-fluoro-3-phenoxyphenyl) propenyl cyclopropane, (Z) -, is obtained in 40% product of 3- [1- (p-chlorophenyl) cyclopropyl] -2-fluoro-2-propen-1-ol, (Z) -. In contrast, WO 94/06741 discloses that 1- (p-chlorophenyl) -l- [2-fluoro-3- (4-fluoro-3-phenoxyphenyl) propenyl] cyclopropane, (Z) - is obtained in 20% of product of 3- [1- (p-chlorophenyl) cyclopropyl] 2-fluoro-2-pro-pen-1-ol, (Z) -.

EXAMPLE 3 Preparation of l-Bromo-4- (p-chlorophenyl) -2-fluoro-4-methyl-2-pentene, (Z) - Under a nitrogen atmosphere, a solution of triphenyl phosphine (0.96 g, 4.25 mmol) in carbon tetrachloride at -5 ° C, is treated as drops with a solution of bromine (0.679 g, 4.25 g. mmol) in carbon tetrachloride, heated and stirred at room temperature for 45 minutes, treated with a solution of 4- (p-chlorophenyl) -2-fluoro-4-methyl-2-penten-1-ol, (Z ) - (0.81 g, 3.54 mmol) in carbon tetrachloride, refluxed for 2 hours, cooled to room temperature, and poured into petroleum ether. The resulting mixture is filtered through diatomaceous earth. The filtrate is washed sequentially with α-gua, saturated sodium hydrogen carbonate solution and saline, dried over anhydrous sodium sulfate, and concentrated in vacuo to obtain an oil. Flash column chromatography of the oil, using silica gel and a 1: 9 solution of ethyl acetate / hexanes, gives the title product as a colorless oil (0.736 g, 71% product), which is identified by analysis of NMR spectrum.

EXAMPLE 4 Preparation of 4- (p-Chlorophenyl) -2-fluoro-1- (4-fluoro-3-phenoxyphenyl) -4-methyl-2-pentene, (Z) - Under a nitrogen atmosphere, a mixture of 1-bromo-4- (p-chlorophenyl) -2-fluoro-4-methyl-2-pentene, (Z) - (320.8 mg, 1.1 mmol), bis (dibenzylideneacetone) palladium (O) (Pd (dba) 2, 31.6 mg, 0.055 mmol) in toluene (8 ml) is treated with potassium carbonate (608 mg, 4.4 mmol), degassed, treated with a solution of 4-fluoro-3-phenoxybenzeneboronic acid (331.8 mg, 1.43 mmol) in ethanol (2 L), refluxed for 45 minutes, cooled to room temperature, and filtered through diatomaceous earth . The filtrate is diluted with ethyl acetate, and the resulting solution is washed sequentially with water and saline, dried over anhydrous sodium sulfate, and concentrated in vacuo to obtain a residue. Flash column chromatography of the residue, using silica gel and a 1: 9 solution of ethyl acetate / hexanes, gives the title product as a colorless liquid (401 mg, 91% product), which is identified by NMR spectrum analysis. As can be seen from the data of Examples 3 and 4, 4- (p-chlorophenyl) -2-fluoro-1- (4-fluoro-3-phenoxyphenyl) -4-methyl-2-pentene, (Z) -, it is obtained in 65% product of 4- (p-chlorophenyl) -2-fluoro-4-methyl-2-penten-1-ol, (Z) -. In contrast, GB 2,288,803-A discloses that 4- (p-chlorophen-lo) -2-fluoro-l- (4-fluoro-1- (4-fluoro-3-phenoxyphenyl) -4-methyl-2-pentene, (Z) -, is obtained in 37% product of 4- (p-chlorophenyl) -2-fluoro-4-methyl-2-penten-1-ol, (Z) -.

EXAMPLE 5 Preparation of 4-Fluoro-3-phenoxybenzeneboronic acid A solution of 5-bromo-2-fluorophenyl ether phenyl (8.01 g, 3 mmol) in tetrahydrofuran is added dropwise to a mixture of magnesium rotations (0.0802 g, 3.3 mmol), a iodine crystal and some drops of 1,2-dibro-moethane in tetrahydrofuran at 50-55 ° C under nitrogen After the addition is complete, the rion mixture is stirred at 50-55 ° C for 70 minutes and cooled to room temperature The cooled mixture is added for 25 minutes to a solution of trimethyl borate (4.09 mL, 3.6 mmol) in diethyl ether at dry ice / acetone bath temperature. After the addition is complete, the mixture is stirred at a dry ice / acetone bath temperature for 20 minutes, allowed to warm to -10 ° C for 25 minutes, sequentially diluted with acetic acid and water, stirred at room temperature for 30 minutes, and extracted with ether.The organic extract is washed with water, dried over anhydrous sodium sulfate, and concent. in vacuo to obtain a residue. A mixture of the residue in water is heated on a steam bath for 30 minutes, cooled to room temperature and filtered to obtain a solid, which is washed with hexanes and dried to give the title product as a colorless solid (5.7 g, mp 177-18? "C, 82% product.) It is noted that with respect to this date, the best method known to the applicant to carry out the said invention, having described the invention as above, • Claims as property what is contained in the following.

Claims (15)

1. A process for the preparation of a fluoroolefin compound, which has the structural formula I (I) wherein R is hydrogen, or C4-alkyl, and R1 is C, -C4, or cyclopropyl, or R and R1 are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C, -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 6 alkoxy or c 1 -C 4 haloalkoxy, or 1 or 2 naphthyl optionally substituted with any combination of from one to three halogen groups. C, -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or haloalkoxy Ar- is phenoxyphenyl optionally substituted with any combination of from one to five halogen groups, C 1 -C 4 alkyl, C 1 -C haloalkyl, C 4 alkoxy, or C 1 -C 4 haloalcoxy, biphenyl optionally substituted with any combination of from one to five halogen groups, C 1 -C 4 alkyl, C haloalkyl, C 4, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy, benzylphenyl optionally substituted with any combination of from one to five halogen groups, C, -C 4 alkyl , haloalkyl C.-C ^ C, -C4 alkoxy, or C1-C4 haloalkoxy, or benzoylphenyl optionally substituted with any combination of from one to five halogen groups, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C haloalkyl. . , C, -C4 alkoxy, or haloalkoxy ^ -C ^ and the configuration of the groups ArCRR- - and -CH2Ar1 on the double bond is predominantly mutually trans, whose process is characterized pQj. to be reacted a 4-aryl-2-fluoro-2-utene-1-ol compound having the structural formula I I (II) wherein Ar, R, and R are as described above, with a brominating agent, to form a compound 4-aryl-l-bromo-2-fluoro-2-butene having the formula is tuctural III (III) wherein Ar, R, and R, are as described above, and the compound of formula III is reacted with a palladium catalyst, a base, and a boron acid having the structural formula IV, an anhydride of boron having the structural formula V, or a borate ester having the structural formula VI (HO), B-Ar. (IV) .B. -B- Ar O Ar (V) (R20) 2B-Ar? (SAW) wherein R2 is 1-C4 alkyl, and Ar ^ is as described above.

2. The process according to claim 1, characterized in that the brominating agent is a bromine / triphenylphosphine complex.

3. The process according to claim 1, characterized in that the palladium catalyst is "selected" -the 9ruP ° ° -ue consisting of bis (dibenzylidene ketone) palladium (O), tetrakis (triphenylphosphine) palladium (O), bis (acetonitrile) palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, [1,4-bis (diphenylphosphine) butane] -palladium (II) dichloride, [1,1'-bis (diphenylphosphine) ferrocene] palladium (II) diacetate, palladium (II) acetate, palladium (II) chloride, and palladium on activated carbon, and mixtures thereof; and the base is selected from the group consisting of an alkali metal carbonate, or an alkaline earth metal carbonate, an alkali metal hydrogen carbonate, a metal hydroxide, and alkaline earth metal hydroxide, an alkoxide C ..- C, alkali metal, thallium carbonate (I), a C.sub.C alkoxide, thallium (i), thallium hydroxide (I), and a tri (C.sub.C.) alkyl amine, and mixtures thereof.

4. The process according to claim 3, characterized in that the palladium catalyst is bis (di-benzylidene ketone) palladium (O), and the base is an alkali metal carbonate.

5. The process according to claim 1, characterized in that the compound of formula III is reacted with a boron acid.

6. The process according to claim 1, characterized in that the step of the first reaction is carried out in a first solvent selected from the group consisting of an aromatic hydrocarbon, a halogenated hydrocarbon, a carboxylic acid amide, a glycol, an alcohol C -, - C4, a ketone, and an ether and mixtures thereof, and mixtures with water.

7. The process according to claim 6, characterized in that the first solvent is a halogenated hydrocarbon, and the second solvent is toluene or a mixture of toluene / ethanol.

8. The process according to claim 1, characterized in that the compound of formula II is reacted with the brominating agent at a temperature of about 50 ° C to 130 ° C, the compound of formula 3 is reacted with the palladium catalyst , the base, and the compound of formula IV, V, or VI at a temperature of about 50 * C to 130 * C.

9. A process for the preparation of a fluoroolefin compound, which has the structural formula I (I) wherein R is hydrogen or alkyl ^ -C ^ and R1 is C, -C4 alkyl, or cyclopropyl, or R and R1 are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or 1 -C 4 haloalkoxy, or 1- or 2-naphthyl optionally substituted with any combination of from one to three halogen groups, C, -C 4 alkyl, C, -C 4 haloalkyl, C 1 C alkoxy, C 1 -C 4 haloalkoxy; Ar. is phenoxyphenyl optionally substituted with any combination of from 1 to 5 halogen groups, C1-C4 alkyl, haloalkyl C.-C. C4-C4 alkoxy, or C1-C4 haloalkoxy, biphenyl optionally substituted with any combination of from one to five halogen groups, C, -C4 alkyl, haloalkyl C.-Cj, - akoxy. C7-C4-C4-cycloalkyl, benzylphenyl optionally substituted with any combination of from one to five halogen groups, C1-C4 alkyl, haloalkyl C.-C4, alkoxy C, -C4, or haloalkyl C.-C4, or benzoylphenyl optionally substituted with any combination of from one to five halogen groups. C.-C.alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 haloalkoxy, and the configuration of the groups ArCRR.sub.1 - and -CH.sub.2 A.sub.1 on the double bond is predominantly mutually trans, the process of which is characterized because it reacts a 4-aryl-l-bromo-2-fluoro-2-butne compound having the structural formula III. (III) wherein Ar, R, and R., are as described above, with about Q.OOI at 0.1 molar equivalent of a palladium catalyst, at least about 2 molar equivalents of a base, and an acid of boron having the structural formula IV, a boron anhydride having the structural formula V, or a borate ester having the structural formula VI (HO) 2B-Ar? (IV) Ar (V) (R20) 2B-Ar? (SAW) wherein R2 is C, -C4 alkyl, and Ar is as described above, at a temperature of about 50-130 ° C in the presence of a solvent.

10. The process according to claim 9, wherein the palladium catalyst is selected from the group consisting of bis (dibenzylidene ketone) palladium (O) te ,. -trakis (triphenylphosphine) palladium (O), bis (acetonitrile) palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, [1,4-bis (diphenylphosphine) butane] palladium (II) dichloride, [1, 1'-bis (diphenylphosphine) ferrocene] palladium (11) diacetate, palladium (II) acetate, palladium (II) chloride. and palladium on activated carbon and mixtures thereof, and the base is selected from the group consisting of an alkali metal carbonate, an alkaline earth metal carbonate an alkali metal hydrogen carbonate, an alkali metal hydroxide, or a hydroxide alkaline earth metal, an alkoxide C.-C, alkali metal, thallium carbonate (I), a 1-C6 alkoxide of thallium (I), thallium hydroxide (I), and a tri (alkyl c? -c) amine , and mixtures thereof.

11. The process according to claim 10, characterized in that the catal-rrlpr of blade-iLo is bis (dibecylidenace -tona) palladium (O), and the base of a carbonate of metal to the -calino.

12. The process according to claim 9.03 is: - selected because it is selected from the group consisting of an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, a carboxylic acid amide, a glycol, an alcohol c? "C4, a ketone, and an ether, and mixtures thereof, and mixtures with water.

13. A compound that has the structural formula characterized in that R is hydrogen, or C 1 -C 4 alkyl, or R and R are taken, together with the carbon atom to which they are attached to form a cyclopropyl group; R1 is C ^ C alkyl. , or cyclopropyl, or R and R1 are taken together with the carbon atom to which they are attached, to form a cyclopropyl group; Ar is phenyl optionally substituted with any combination of from one to three halogen groups, C, -C alkyl. , C ^ -C ^ haloalkyl, C-, C4-alkoxy, or C1-C4-haloalkoxy; or 1- or 2-naphthyl optionally substituted with any combination of from one to three halogen groups, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 6 alkoxy, or C 1 -C 4 haloalkoxy and fa configuration of the groups ArCRR1-y-CH2BR on the double bond is predominantly mutually trans.

14. The compound according to claim 13, selected from the group consisting of l- (p-chlorophenyl) -l- (3-bromo-2-fluoropropenyl) cyclopropa, no, (Z) -; and l-bromo-4- (p-chlorophenyl) -2-f luoro-4-methyl-2-pentene, (Z) -.

15. A process for preparing a compound according to claim 13, whose process is characterized by reacting a 4-aryl-2-fluoro-2-buten-1-ol compound having the structural formula II wherein R, R., Ar are as defined in claim 13, with a brominating agent selected from the group consisting of bromo-triphenylphosphine complex, phosphorus tribromide, thionyl bromide, HBr, and mixtures thereof, in a solvent at a temperature of about 50-130 ° C.