PROCESS AND INTERMEDIATE COMPOUNDS FOR THE PREPARATION OF PESTI- CIDAL FLUOROOLEFIN COMPOUNDS The present invention provides a two-step process for the prepa- ration of pesticidal fluoroolefin compounds of formula I wherein R is hydrogen or C1-C4-alkyl, and R1 is C1-C4-alkyl or cyclopropyl, or R and RI are taken together with the carbon atom to which they are attached to form a cyclopropyl group; Ar is phenyl which is unsubstituted or substituted with any com- bination of from one to three halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, or 1-or 2-naphthyl which is unsubstituted or substituted with any combination of from one to three halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups; Arl is. phenoxyphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, biphenyl which is unsubstituted or substituted with any com- bination of from one to five halogen, C1-C4-alkyl, C1-C4-halo- alkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, phenyl which is unsubstituted or substituted with any combi- nation of from one to five halogen, C1-C4-alkyl, C1-C4-halo- alkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, benzylphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, or benzoylphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or Cl-C4-haloalkoxy groups,

which comprises reacting fluorobromoolefin compounds of formula II wherein Ar, R and R1 are as described above, with organozinc compounds of formula III or IV BrZnCH2Ar1 Zn (CH2Arl) 2 III IV wherein Arl is as described above, in the presence of a palladium catalyst and a solvent, which compounds of formula II are obtained by reacting aldehyde compounds of formula V wherein Ar, R and R1 are as defined above, with (a) fluorotribromomethane, (b) a tri (substituted) phosphine or a hexaalkylphosphoramide or a mixture thereof, and (c) zinc, in the presence of a solvent.

In compounds of formula I, the configuration of the groups ArCRR1- and-CH2Arl about the double bond is preferably predominately mu- tually trans."Predominately trans"means that the trans-compound is present at a percentage of at least 80%, preferably above 95%.

The present invention also relates to the fluorobromoolefin com- pounds of formula II.

Pesticidal fluoroolefin compounds and processes for their prepa- ration are described in WO 94/06741 and GB-A 2 288 803.

However, those processes are not entirely statisfactory because the fluoroolefin compounds are produced in relatively low yields from multi-step processes.

It was therefore an object of the present invention to provide an improved process for the preparation of fluoroolefin compounds.

Accordingly, a two-step overall process for the preparation of fluoroolefin compounds of formula I starting form aldehyde compounds of formula V, via intermediate compounds of formula II, has been found.

Furthermore, compounds of formula II have been found.

Advantageously, the inventive process affords compounds of for- mula I which are predominately in the trans-configuration.

WO 94/06741 and GB-A 2 288 803 disclose that fluoroolefin compounds are obtained in four steps starting from aldehyde compounds of formula V.

Exemplary of halogen hereinabove are fluorine, chlorine, bromine and iodine; The term"alkyl"is defined as a saturated, straight or branched chain hydrocarbon with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl- propyl and 1,1-dimethyl-propyl.

The term"alkoxy"is defined as a saturated, straight or branched chain hydrocarbon with 1 to 4 carbon atoms (as described above) which is bond to the backbone via an oxygen (-O-) atom; The term"haloalkyl"is defined as an alkyl group, as defined above, wherein the hydrogen atoms may be partially or totally substituted with halogen atoms as defined above, wherein the ha- logen atoms may be the same or different, for example C1-C2-halo- alkyl such as chloro-methyl, bromomethyl, dichloro-methyl, trich- loro-methyl, fluoro-methyl, difluoro-methyl, trifluoro-methyl, chloro-fluoro-methyl, dichlorofluoro-methyl, chloro-difluoro-me- thyl, 1-chloro-ethyl, 1-bromo-ethyl, 1-fluoro-ethyl, 2-fluoro- ethyl, 2, 2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, 2-chloro-2- fluoro-ethyl, 2-chloro-2,2-difluoro-ethyl, 2,2-dichloro-2-fluoro- ethyl, 2,2,2-trichloro-ethyl and pentafluoro-ethyl, wherein the halogen atoms may be the same or different.

The term"haloalkoxy"is defined as an alkoxy group as defined above, wherein the hydrogen atoms may be partially or totally substituted with one or more halogen atoms as defined above, whe- rein the halogen atoms may be the same or different.

Wavy lines in structural formulae depict the carbon-carbon double bond in both the E-or the Z-isomeric configuration.

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

In a preferred embodiment of the present invention, a fluorobro- moolefin of formula II is reacted with at least one molar equiva- lent, such as 1 to 2 molar equivalents, of an organozinc compound of formula III or IV, and 0,001 to 0,2, preferably 0,01 to 0,1 molar equivalent of a palladium catalyst in the presence of a solvent, preferably in a temperature range of-70°C to 70°C.

The product compounds of formula I may be isolated by diluting the reaction mixture with water and extracting the product with a suitable extraction solvent. In the isolation procedure, conven- tional. extraction solvents such as ether, ethyl acetate, toluene, and dichloromethane may be utilized.

Preferred palladium catalysts for use in the present invention include, but are not limited to, bis (dibenzylideneace- tone) palladium (0), tetrakis (triphenylphosphine) palladium (0), bis (acetonitrile) palladium (II) chloride, bis (triphenylphosp- hine) palladium (II) chloride, [1,4-bis (diphenylphosphine) bu- tane] palladium (II) dichloride, [1, l'-bis (diphenylphosphino) ferro- cene] palladium (II) diacetate, palladium (II) acetate, palladium (II) chloride and mixtures thereof.

Preferred solvents for use in the preparation of compounds of formula I include, but are not limited to, aromatic hydrocarbons such as toluene, benzene, xylenes and mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene, carboxylic acid amides, such as N, N-dimethylformamide, ethers such as tetrahydrofuran and dioxane, and halogenated hydrocarbons such as chloroform and carbon tetrachloride, and mixtures the- reof.

Preferred solvents for use in the preparation of compounds of formula I include carboxylic acid amides and ethers and mixtures thereof, preferably N, N-dimethylformamide and tetrahydrofuran and mixtures thereof.

In a preferred embodiment of the present invention for the prepa- ration of fluorobromoolefin compounds of formula II, aldehyde compounds of formula V are reacted with at least one molar equi- valent, such as 2 to 6 molar equivalents, of fluorotribromome- thane, and at least one molar equivalent, such as 2 to 7 molar equivalents, of a tri (substituted) phosphine, and at least one mo-

lar equivalent, such as 1 to 4 molar equivalents, of zinc, prefe- rably zinc dust, in the presence of a solvent, preferably in a temperature range of-20°C to 70°C.

Preferred tri (substituted) phosphines for use in this invention. include, but are not limited to, triaryl-phosphines such as tri- phenylphosphine or tri-p-tolyl-phosphine, and tri (branched C3-C6-alkyl)-phosphines such as triisopropylphosphine or triter- tiarybutylphosphine, and mixtures thereof.

Preferred tri (substituted) phosphines which produce compounds of formula II with a preferred ratio of (E): (Z)-isomer include trii- sopropylphosphine and tritertiarybutylphosphine. Preferred ratios of (E): (Z)-isomer of formula II are ratios above 1,5: 1, prefera- bly above 2,5: 1, more preferably above 3,5: 1 (E): (Z).

Preferred hexaalkylphosphoramides for use in the present inven- tion include hexamethylphosphoramide or hexaethylphosphoramide, and mixtures thereof.

Preferred solvents for use in the preparation of fluorobromoole- fins of formula II include, but are not limited to, ethers such as diethyl ether or tetrahydrofuran and halogenated hydrocarbons such as dichloromethane, and mixtures thereof.

More preferred solvents for use in the preparation of fluorobro- moolefins of formula II include diethyl ether, tetrahydrofuran and dichloromethane, and mixtures thereof.

Starting organozinc compounds of formulae III and IV may be pre- pared by reacting a bromide compound of formula VI BrCH2Arl VI wherein Arl is described above, with activated zinc (e. g., Rieke zinc) in the presence of a solvent such as tetrahydrofuran.

Aldehyde compounds of formula V may be prepared using conventio- nal procedures known in the art, see for example: Bioorg. Med.

Chem. Lett. (1998), 8 (3), p. 301; Chem. Pharm. Bull. (1996), 44 (10), p. 1858; Tetrahedron Lett. (1996), 37 (5), 2629; J. Org.

Chem. Soc. (1995), 60 (18), p. 5803; and J. Am. Chem. Soc.

(1993), 115, p. 3030.

Preferred fluoroolefin compounds of formula I which may be prepa- red by the process of the present invention are those wherein the variables have the following meanings, each alone or in combina- tion: Preferred are compounds of formula I wherein R is hydrogen and R1 is isopropyl or cyclopropyl ; Also preferred are compounds of formula I wherein R and R1 are methyl; Furthermore, preferred are compounds of formula I wherein R and are taken together with the carbon atom to which they are atta- ched to form a cyclopropyl group.

Preferred are compounds of formula I wherein Ar is phenyl which is unsubstituted or substituted with any combination of from one to three halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups.

More preferred are compounds of formula I wherein Ar is phenyl which is unsubstituted or substituted with any combination of from one to three halogen, preferably chlorine of fluorine.

Most preferred are compounds of formula I wherein Ar is 4-chloro- phenyl.

Moreover, compounds of formula I are preferred wherein Arl is '3-phenoxyphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, # 3-Diphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups, or phenyl which is unsubstituted or substituted with any combi- nation of from one to five halogen, C1-C4-alkyl, C1-C4-halo- alkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups.

More preferred are compounds of formula I wherein Ar1 is 3-phe- noxy-phenyl which is unsubstituted or substituted with any com- bination of from one to five halogen, C1-C4-alkyl, C1-C4-halo- alkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups.

Especially preferred are compounds of formula I wherein Ar1 is 3-phenoxyphenyl which is unsubstituted or substituted with any combination of from one to six halogen, preferably fluorine.

Most preferred compounds of formula I agents are those wherein R is hydrogen and R1 is isopropyl or cyclopropyl, or R and RI are methyl, or R and R1 are taken together with the carbon atom to which they are attached to form a cyclopropyl group; and Ar is phenyl which is unsubstituted or substituted with any com- bination of from one to three halogen, C1-C4-alkyl, Ci-C4-halo- alkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups; and Arl is 3-phenoxyphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy groups.

Preferred fluorobromoolefin compounds of formula II are those wherein R, R1 and Ar are as defined above for preferred compounds of formula I.

In a preferred embodiment of this invention, compounds of formula II are in the (E)-configuration.

Preferred compounds of formulae III, IV and V for use in the in- ventive process are those wherein the variables Ar, R, and R1, respectively, are as defined above for preferred compounds of for- mula I.

EXAMPLE 1 Preparation of (Z)-1-(p-Tolyl)-1-[2-fluoro-3-(3-phenoxy- phenyl)-1-propenyl] cyclopropane,

Under a nitrogen atmosphere, a mixture of 1-(2-bromo-2-fluoroe- thene)-l- (p-tolyl) cyclopropane, (E)-to (Z)-ratio 5: 3 (0,5 g, 2 mmol), tetrakis (triphenylphosphine)-palladium (O) (0,2 g, 0,2 mmol), and tetrahydrofuran (20 ml) was treated with a 3-phe- noxybenzylzinc bromide solution (prepared from 3-phenoxybenzyl- bromide (1,1 g, 4 mmol) and Rieke zinc (3,25 ml of a 1,5 molar solution in tetrahydrofuran), and tetrahydrofuran 20 ml). The re- sultant reaction mixture was stirred at room temperature until the reaction was complete as followed by gas chromatography ana- lysis, diluted with water, and extracted with ethyl acetate. The organic extract was dried over anhydrous magnesium sulfate, and concentrated in vacuo to obtain a-residue. Column chromatography of the residue using silica gel and heptane gave the title product (0,18 g) predominately in the (Z)-configuration.

Using essentially the same procedure, the following compounds are obtained predominately in the (Z)-configuration:

EXAMPLE 2 Preparation of (Z)-4- (p-Chlorophe- nyl)-2-fluoro-5-methyl-l- (3-phenoxyphenyl)-2-hexene, Under a nitrogen atmosphere, a mixture of 1-bromo-3-(p-chlorophe- nyl)-1-fluoro-4-methyl-1-pentene, (E)-and (Z)- (0,9 g, 3,1 mmol), tetrakis (triphenylphosphine)-palladium (0) (0,25 g, 0,22 mmol), and N, N-dimethyl-formamide (20 ml) was treated with 5 ml of a 3-phenoxybenzylzinc bromide solution (prepared from 3-phenoxybenzyl bromide (1,3 g, 5,4 mmol) and Rieke zinc (4 ml of a 1,5 molar solution in tetrahydrofuran), and tetrahydrofuran 20 ml). The resultant reaction mixture was stirred at room temperature for one hour, treated with an additional 5 ml of the 3-phenoxybenzylzinc bromide solution, stirred at room temperature, and poured into 2 N hydrochloric acid solution. The resultant aqueous mixture was extracted with diethyl ether. The organic extract was dried over anhydrous magnesium sulfate, and concentrated in vacuo to obtain a residue. Column chromatography of the residue using silica gel, and 100: 1 and 200: 1 hexane/ethyl acetate solutions gave the title product (0,35 g) predominately in the (Z)-configuration.

Following essentially the same procedure, but using the appro- priate palladium catalyst, the following compounds are obtained predominately in the (Z)-configuration:

Pd Catalyst Ar R R1 Arl EXAMPLE 3 Preparation of (E)-and (Z)-l- (2-Bromo-2-fluoroethene)-l- (p- chlorophenyl) cyclopropane, CHO Cl < FCBr3 + Zn + [CH (CH3b] 3P C1 T F diethyl ether (E)-and (Z)- (4: 1) A mixture of 1-carboxalidehyde-1-(p-chlorophenyl)-cyclopropane (0,2 g, 1,1 mmol), fluorotribromomethane (0,39 ml, 1, 08g, 4 ; 0 mmol), zinc dust (0,12 g, 1,8 mmol), triisopropylphosphine (0, 75 ml, 3,9 mmol), and diethyl ether (20 ml) was stirred at room temperature for one hour, treated with additional triisopro- pylphosphine (0,3 ml, 1,6 mmol) to give the title product having

an (E)-to (Z)-isomer ratio of 4: 1. This reaction is listed as reaction no. 1 in Table I.

Following essentially the same procedure, but varying the phosphine and solvent, 1-(2-bromo-2-fluoroethene)-1-(p-chlorophe- nyl) cyclopropane, (E)-and (Z)-is obtained in the ratios shown below in Table I.

As can be seen from the data in Table I, the (E)-isomer of 1- (2-bromo-2-fluoroethene)-1- (p-chlorophenyl) cyclopropane is ob- tained in significantly greater amounts relative to the (Z)-iso- mer when the phosphine'is triisopropylphosphine or tritertiarybu- tylphosphine.

Table I CHO + FCBr3 + Zn + phosphine ci solvent F Br I Br and I F //Z _ C1 (E)-C1 t) Product Ratio Phosphine Solvent (E:Z 1 [CH(CH3)2]3P diethyl ether 4:1 2 [(CH2) 3CH3] 3P diethyl ether No Reaction 3 (C6H5) 3P diethyl ether No Reaction 4 [CH (CH3) 2] 3P dichloromethane 1,7: 1 5 [C (CH3) 3] 3P dichloromethane 2: 1 6 (C2H5) 3P dichloromethane No Reaction 7 (CH3) 3P dichloromethane No Reaction 8 (C6H5) 3P dichloromethane 1: 1.4 9 [CH (CH3) 2]3P. tetrahydrofuran 2, 5: 1 10 [(CH2)3CH3]3P tetrahydrofuran No Reaction 11 (CH3) 3P tetrahydrofuran No Reaction 12 (C6H5) 3P tetrahydrofuran 1: 1

EXAMPLE 4 Preparation of (E)-and (z)-1_(2-Bromo-2-fluoroethene)-1-(p-to- lyl) cyclopropane, \ CHO 1 J + FCBrg + Zn + [CH (ci3) z 73 P CH3 ,,, e F diethyl ether I Br CH3 (E)-and (Z)- (3,6: 1) Following essentially the same procedure as described in Example 3, but using the reactants shown above, the title product is ob- tained having an (E)-to (Z)-isomer ratio of 3,6: 1.

EXAMPLE 5 Following essentially the same procedure as described in Example 3, the following compounds are obtained: Product Ratio (E:Z) W R R1 Phosphine Solvent Cl CH (CH3) 2 H (C6H5) 3P dichloro-2: 1 methane F CH3 CH3 (C6H5) 3P tetra-2: 1 hydrofuran F-CH2-CH2- (C6H5) 3p tetra-1 : 1 hydrofuran Cl CH3 CH3 (C6H5) 3P dichloro-1: 1,3 methane